EP4073205A1 - Aromatic isothiocyanates - Google Patents

Aromatic isothiocyanates

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Publication number
EP4073205A1
EP4073205A1 EP20819753.3A EP20819753A EP4073205A1 EP 4073205 A1 EP4073205 A1 EP 4073205A1 EP 20819753 A EP20819753 A EP 20819753A EP 4073205 A1 EP4073205 A1 EP 4073205A1
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Prior art keywords
denotes
compounds
atoms
pct
unfluorinated
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EP20819753.3A
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German (de)
French (fr)
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EP4073205B1 (en
Inventor
Constanze Brocke
Dmitry USHAKOV
Dagmar Klass
Carsten FRITZSCH
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
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    • C09K19/00—Liquid crystal materials
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    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/181—Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/183—Ph-Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C09K2019/3063—Cy-Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/11—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the High Frequency technical field

Definitions

  • the present invention relates to aromatic isothiocyanates, liquid-crystalline media comprising same, and to high-frequency components comprising these media, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas (e.g. phased array antennas), and to devices comprising said components.
  • microwave components for high-frequency devices such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas (e.g. phased array antennas), and to devices comprising said components.
  • Liquid-crystalline media have a been used for many years in electro-optical displays (liquid crystal displays: LCDs) in order to display information. More recently, however, liquid-crystalline media have also been proposed for use in components for microwave technology, such as, for example, in DE 102004029429.1 A and in JP 2005- 120208 (A).
  • Fluorine atoms are commonly used in mesogenic compounds to introduce polarity. Especially in combination with a terminal NCS group high dielectric anisotropy values can be achieved.
  • compositions available for the use in microwave applications are still afflicted with several disadvantages. It is required to improve these media with respect to their general physical properties, the shelf life and the stability under operation in a device.
  • An object of the present invention is to provide a compound for the use in liquid crystalline media with improved properties relevant for the application in the microwave range of the electromagnetic spectrum.
  • a compound of formula C shown below is provided and a liquid crystalline medium comprising the compound.
  • the present invention relates to a compound of formula C
  • R c denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more Chh-groups may
  • R p denotes halogen, CN, NCS, R F , R F -0- or R F -S-, wherein
  • R F denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms
  • X denotes Cl or F, preferably F
  • Y denotes H, Cl, F, alkyl or alkoxy each having 1 to 6 C atoms, preferably, H, F,
  • ⁇ — t denote a radical selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-
  • 10 or more non-adjacent CH 2 groups may be replaced by -O- and/or -S- and in which one or more H atoms may be replaced by F, c) the group consisting of thiophene-2, 5-diyl, thieno[3,2-b]thiophene-2,5- diyl, selenophene-2, 5-diyl, each of which may also be mono- or polysubstituted by L, wherein
  • the present invention further relates to a compound of formula N
  • the present invention further relates to a liquid-crystalline medium comprising a compound of formula C and to the use of a liquid-crystalline medium comprising a compound of formula C in a component for high-frequency technology.
  • a component and a device comprising said component, both operable in the microwave region of the 21/116080 PCT/EP2020/085026
  • Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuits and adaptive filters.
  • liquid-crystalline media having excellent stability and at the same time a high dielectric anisotropy, suitably fast switching times, a suitable, nematic phase range, high tunability and low dielectric loss, by using compounds of formula C in liquid-crystalline media.
  • the media according to the present invention are distinguished by a high clearing temperature, a broad nematic phase range and excellent low-temperature stability (LTS). As a result, devices containing the media are operable under extreme temperature conditions.
  • LTS low-temperature stability
  • the media are further distinguished by high values of the dielectric anisotropy and low rotational viscosities.
  • the threshold voltage i.e. the minimum voltage at which a device is switchable, is very low.
  • a low operating voltage and low threshold voltage is desired in order to enable a device having improved switching characteristics and high energy efficiency.
  • Low rotational viscosities enable fast switching of the devices according to the invention.
  • high-frequency technology means applications of electromagnetic radiation having frequencies in the range of from 1 MHz to 1 THz, preferably from 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, particularly preferably from about 5 GHz to 150 GHz.
  • halogen is F, Cl, Br or I, preferably F or Cl, particularly preferably F. P19228 AT
  • alkyl is straight-chain or branched and has 1 to 15 C atoms, is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.
  • branched alkyl is preferably isopropyl, s-butyl, isobutyl, isopentyl, 2- methylbutyl, 2-methylhexyl or 2-ethylhexyl.
  • an alkoxy radical is straight-chain or branched and contains 1 to 15 C atoms. It is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C
  • an alkenyl radical is preferably an alkenyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one C-C double bond. It is
  • the alkenyl radical can be in the form of E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred.
  • the alkenyl radicals are preferably vinyl, prop-1- or -2-enyl, but-1 -, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl.
  • the alkenyl radical can be in the form of E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred.
  • the alkenyl radicals are preferably vinyl, prop-1- or -2-enyl, but-1 -, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl,
  • prop-2-enyl, but-2- and -3-enyl, and pent-3- and -4-enyl are particularly preferred.
  • alkynyl is taken to mean an alkynyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one C-C triple bond.
  • 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.
  • R F denotes a halogenated alkyl-, alkoxy-, alkenyl or alkenyloxy it can be branched or unbranched. Preferably it is unbranched, mono- poly or perfluorinated, preferably perfluorinated and has 1, 2, 3, 4, 5, 6 or 7 C atoms, in case of alkenyl 2, 3, 4, 5, 6 or 7 C atoms.
  • the compounds of the general formula C are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme- Verlag, Stuttgart), to be precise under reaction conditions which are known and are suitable for said reactions. Use can be made here of variants which are known per se, but are not mentioned here in greater detail.
  • the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead by immediately reacting them further into the compounds of the general formula C.
  • Preferred intermediates are 4-bromo-2,6-dichloroaniline and 4-bromo-2-chloro-6- fluoroaniline, both described in the literature, which can be reacted to give compounds of the formula N for example by cross coupling reactions commonly known as Suzuki, Stille, Sonogashira reactions, and the like.
  • Preferred pathways are exemplified in schemes 1 and 2, in which the groups and parameters have the meanings defined in claim 1.
  • Preferred reagents for the process according to the invention for the transformation of compounds of the formula N into compounds of the formula C are carbon disulfide, thiophosgene, thiocarbonyl diimidazole, di-2-pyridyl thionocarbonate, bis(dimethylthiocarbamoyl) disulfide, dimethylthiocarbamoyl chloride and phenyl chlorothionoformate, very preferably thiophosgene.
  • R c denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl
  • PCT/EP2020/085026 8 may be replaced preferably alkyl having 1 to 12 C atoms.
  • R c denotes R p
  • R p denotes halogen, CN, NCS, R F , R F -0- or R F -S-
  • R F denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms, preferably CF 3 or OCF 3
  • f formula C are preferably selected from the compounds in which the
  • L 1 and L 2 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms, and where the other groups and parameters have the meanings given above.
  • the compounds of formula C are selected from the compounds of the formulae C-1 to C-11 : PCT/EP2020/085026 P19228 AT
  • L 1 , L 2 and L 3 identically or differently, denote H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and
  • R c and X have the meanings given above and preferably R c denotes alkyl having 1 to 7 C atoms or a group R p ,
  • R p preferably denotes perfluorinated alkoxy having 1 to 7 C atoms, and X denotes F.
  • one of the groups Z C1 and Z C2 of formula C denotes a single bond and the other one of Z C1 and Z C2 denotes -CoC-.
  • Very preferred compounds of the formula C are selected from the compounds of the following sub-formulae: P19228 AT
  • R c has the meanings given above and preferably denotes alkyl having 1 to 7 C atoms or CF 3 O.
  • Very particularly preferred compounds are the compounds of the formulae C-7-1, C-9- 1, C-9-4, C-10-1, C-10-2, C-10-3, C-10-4, C-10-5, C-10-6, and C-10-7.
  • the medium comprises one or more compounds selected from the group of compounds of the formulae I, II and III,
  • R 1 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluorinated
  • alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, in which one or more Chh-groups may be replaced by preferably unfluorinated alkyl or unfluorinated alkenyl,
  • 25 n is 0, 1 or 2, to on each occurrence, independently of one another, denote
  • R 2 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluori
  • 35 preferably unfluorinated alkyl or unfluorinated alkenyl, P19228 AT
  • R L on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H, and wherein
  • R 3 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluori nated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, in which one or more CFh-groups may
  • R L on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H, and wherein
  • R L preferably denotes H. P19228 AT
  • the compounds of formula I are selected from the group of compounds of the formulae 1-1 to I-5: in which
  • R 1 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
  • the media preferably comprise one or more compounds of formula 1-1 , which are preferably selected from the group of the compounds of the formulae 1-1 a to 1-1 d, preferably of formula 1-1 b: P19228 AT
  • R 1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
  • the media preferably comprise one or more compounds of formula I-2, which are preferably selected from the group of the compounds of the formulae l-2a to l-2e, preferably of formula l-2c:
  • R 1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
  • the media preferably comprise one or more compounds of formula I-3, which are preferably selected from the group of the compounds of the formulae l-3a to l-3d , particularly preferably of formula l-3b: in which R 1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
  • the media preferably comprise one or more compounds of formula I-4, which are preferably selected from the group of the compounds of the formulae l-4a to l-4e, particularly preferably of formula l-4b: in which R 1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C
  • the media preferably comprise one or more compounds of formula I-5, which are preferably selected from the group of the compounds of the formulae l-5a to l-5d, particularly preferably of formula l-5b:
  • R 1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
  • the media preferably comprise one or more compounds of formula II, which are preferably selected from the group of the compounds of the formulae 11-1 to II-3, preferably selected from the group of the compounds of the formulae 11-1 and II-2:
  • R 2 denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or
  • n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula 11-1 are preferably selected from the group of the compounds of the formulae 11-1 a to 11-1 e: in which
  • the compounds of formula II-2 are preferably selected from the group of the compounds of the formulae ll-2a and ll-2b: P19228 AT
  • 15 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula II-3 are preferably selected from the group of the compounds of the of formulae ll-3a to ll-3d:
  • 10 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula III are preferably selected from the group of the compounds of the formulae II 1-1 to NI-6, more preferably of the formulae selected from the group of the compounds of the formulae NI-1, NI-2, NI-3 and NI-4, and particularly preferably of in which
  • one of Z 31 and Z 32 may denote -CoC- and the other groups have the meaning given above under formula III, P19228 AT
  • R 3 denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms, and one of
  • z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula 111-1 are preferably selected from the group of the 25 compounds of the formulae II 1-1 a to 111-1 k, more preferably selected from the group of the compounds of the formulae lll-1a, 111-1 b, 111-1 g and lll-1h, particularly preferably of formula 111-1 b and/or lll-1h: P19228 AT
  • n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5
  • z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula III-2 are preferably compounds of formula lll-2a to III-2I, very preferably II l-2b and/or 111 -2j :
  • n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of formula 111-5 are preferably selected from the compounds of formula P19228 AT
  • R 3 has the meaning indicated above for formula III-5 and preferably denotes C n f i, in which n denotes an integer in the range from 0 to 7, preferably in the range from 1 to 5.
  • the media according to the invention comprise one or more compounds selected from the group of compounds of the formulae IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2:
  • R 1 denotes alkyl or alkenyl having up to 7 C atoms, preferably ethyl, n-propyl, n- butyl or n-pentyl, n-hexyl,
  • R L on each occurrence denotes alkyl or alkenyl having 1 to 5 C atoms, or cycloalkyl or cycloalkenyl each having 3 to 6 C atoms, preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl, very preferably ethyl, P19228 AT
  • liquid-crystalline media according to the present invention in a certain embodiment, which may be the same or different from the previous preferred embodiments preferably comprise one or more compounds of formula IV, IV in which
  • L 4 denotes H or alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6
  • C atoms or cycloalkenyl having 4 to 6 C atoms preferably CH 3 , C2H5, A7-C3H7, /-C3H7, cyclopropyl, cyclobutyl, cyclohexyl, cyclopent-1-enyl or cyclohex- 1-enyl, and particularly preferably CH 3 , C2H5, cyclopropyl or cyclobutyl, denotes H, alkyl having 1 to 3 C atoms or halogen, preferably H, F or Cl, more preferably H or F and very particularly preferably F,
  • R 41 to R 44 independently of one another, denote unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 15 C atoms, unfluorinated
  • alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl each having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl, each having up to 15 C atoms, and alternatively one of R 43 and R 44 or both also denote H, preferably R 41 and R 42 , independently of one another, denote unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each
  • R 41 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each having 2 to 7 C atoms, and particularly preferably P19228 AT
  • R 42 denotes unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 7 C atoms, and preferably
  • R 43 and R 44 denote H, unfluorinated alkyl having 1 to 5 C atoms, unfluorinated cycloalkyl or cycloalkenyl having 3 to 7 C atoms, unfluorinated alkylcyclohexyl or unfluorinated cyclohexylalkyl, each having 4 to 12 C atoms, or unfluorinated alkylcyclohexylalkyl having 5 to 15 C atoms, particularly preferably cyclopropyl, cyclobutyl or cyclohexyl,
  • R 43 and R 44 denotes n-alkyl, particularly preferably methyl, ethyl or n-propyl, and the other denotes H or n-alkyl, particularly preferably H, methyl, ethyl or n-propyl.
  • the liquid-crystal medium additionally comprises one or more compounds selected from the group of compounds of the formulae V, VI, VII, VIII and IX: in which
  • L 51 denotes R 51 or X 51 ,
  • L 52 denotes R 52 or X 52 .
  • R 51 and R 52 independently of one another, denote H, unfluorinated alkyl or
  • alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated alkenyl,
  • X 51 and X 52 independently of one another, denote H, F, Cl, -CN, SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and independently of one another, denote preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and independently of one another, denote preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and independently of one another, denote preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and independently of one another, denote preferably
  • L 62 denotes R 62 and, in the case where Z 61 and/or Z 62 denote trans-
  • R 61 and R 62 independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or P19228 AT
  • X 61 and X 62 independently of one another, denote F or Cl, -CN, SFs, fluorinated alkyl or alkoxy having 1 to 7 C atoms or fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms, one of
  • L 71 denotes R 71 or X 71 ,
  • _72 denotes R 72 or X 72 ,
  • R 71 and R 72 independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably
  • X 71 and X 72 independently of one another, denote H, F, Cl, -CN, -NCS, -SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated or fluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms,
  • R 81 and R 82 independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to
  • I _ 91 denotes R 91 or X 91 ,
  • L 92 denotes R 92 or X 92 , P19228 AT
  • R 91 and R 92 independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to
  • X 91 and X 92 independently of one another, denote H, F, Cl, -CN, -NCS, -SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated or fluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms,
  • the liquid-crystal medium comprises one or more compounds of the formula V, preferably selected from the group of the compounds of the formulae V-1 to V-3, preferably of the formulae V-1 and/or V-2 and/or V-3, preferably of the formulae V-1 and V-2:
  • R 51 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms,
  • R 52 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms or unfluorinated alkoxy having 1 to 7 C atoms,
  • X 51 and X 52 independently of one another, denote F, Cl, -OCF 3 , -CF 3 , -CN or -SF5, preferably F, Cl, -OCF 3 or -CN.
  • the compounds of the formula V-1 are preferably selected from the group of the compounds of the formulae V-1a to V-1d, preferably V-1c and V-1d :
  • Y 51 and Y 52 in each case independently of one another, denote H or F, and preferably
  • R 51 denotes alkyl or alkenyl
  • X 51 denotes F, Cl or -OCF 3 .
  • the compounds of the formula V-2 are preferably selected from the group of the compounds of the formulae V-2a to V-2e and/or from the group of the compounds of the formulae V-2f and V-2g: P19228 AT
  • Y 51 and Y 52 denotes H and the other denotes H or F, preferably likewise denotes H.
  • the compounds of the formula V-3 are preferably compounds of the formula V-3a:
  • X 51 denotes F, Cl, preferably F,
  • X 52 denotes F, Cl or -OCF 3 , preferably -OCF 3 .
  • the compounds of the formula V- 1a are preferably selected from the group of the
  • R 51 has the meaning indicated above and preferably denotes Cnf i, in which
  • 20 n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
  • the compounds of the formula V-1b are preferably compounds of the formula V- 1 b- 1 :
  • RS1 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
  • the compounds of the formula V-1c are preferably selected from the group of the compounds of the formulae V-1c-1 to V-1c-4, particularly preferably selected from the group of the compounds of the formulae V-1c-1 and V-1c-2:
  • R 51 has the meaning indicated above and preferably denotes C n f i, in which n denotes an integer in the range from 1 to 7, preferably in the range from
  • the compounds of the formula V-1d are preferably selected from the group of the compounds of the formulae V-1d-1 and V-1d-2, particularly preferably the compound of the formula V-1d-2:
  • R 51 has the meaning indicated above and preferably denotes C n H 2n+i , in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
  • the compounds of the formula V-2a are preferably selected from the group of the compounds of the formulae V-2a-1 and V-2a-2, particularly preferably the compounds of the formula V-2a-1 :
  • Preferred compounds of the formula V-2b are the compounds of the formula V-2b-1 : P19228 AT
  • R 51 has the meaning indicated above and preferably denotes C n H 2n+i or
  • R 52 has the meaning indicated above and preferably denotes C m H 2m+i or
  • n and m independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • R 51 is, in particular, C n H 2n+i and C m H 2m+i .
  • Preferred compounds of the formula V-2c are the compounds of the formula V-2c-1:
  • R 51 has the meaning indicated above and preferably denotes C n H 2n+i or
  • R 52 has the meaning indicated above and preferably denotes C m H 2m+i or
  • n and m independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • Preferred compounds of the formula V-2d are the compounds of the formula V-2d-1 :
  • n and m independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • (R 51 and R 52 ) is, in particular, (C n H 2n+i and C m H 2m+i ).
  • Preferred compounds of the formula V-2e are the compounds of the formula V-2e-1 : in which
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • (R 51 and R 52 ) is, in particular, (C n H 2n +i and 0-CmH 2m+ i).
  • Preferred compounds of the formula V-2f are the compounds of the formula V-2f-1 : in which
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 51 and R 52 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • Preferred compounds of the formula V-2g are the compounds of the formula V-2g-1 :
  • R 51 has the meaning indicated above and preferably denotes C n H 2n+i
  • z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 51 and R 52 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and 0-C m H 2m+i ).
  • the compounds of the formula VI are preferably selected from the group of the compounds of the formulae VI-1 to VI-5:
  • R 61 and R 62 independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms,
  • X 62 denotes F, Cl, -OCF 3 or -CN
  • the compounds of the formula VI-1 are preferably selected from the group of the compounds of the formulae VI-1 a and VI-1 b, more preferably selected from
  • R 61 has the meaning indicated above and preferably denotes Cnf i
  • (R 61 and R 62 ) are, in particular, (C n f i and C m H2m+i) and (C n H2n+i and 0-C m H2m +i ), in the case of formula Vl-1a particularly preferably (C n H2 n+i and C m H2 m+i ) and in the case of formula VI-1 b particularly
  • the compounds of the formula VI-3 are preferably selected from the compounds of the formula Vl-3a to Vl-3e:
  • R 61 has the meaning indicated above and preferably denotes C n H 2n+i , in which
  • 35 n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 5, and
  • X 62 denotes -F, -Cl, -OCF 3 , or -CN.
  • the compounds of the formula VI-4 are preferably selected from compounds of the for mulae Vl-4a to Vl-4e:
  • R 61 has the meaning indicated above and preferably denotes C n f i, in which n denotes an integer in the range from 1 to 7, preferably in the range
  • X 62 denotes F, Cl, OCF 3 , or -CN.
  • the compounds of the formula VI-5 are preferably selected from the compounds of the
  • Vl-5a to Vl-5d preferably Vl-5b: P19228 AT
  • R 61 has the meaning indicated above and preferably denotes C n f i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 5, and
  • X 62 denotes -F, -Cl, -OCF 3 , or -CN, particularly preferably -OCF 3 .
  • the compounds of the formula VII are preferably selected from the group of the compounds of the formulae VI 1-1 to VII-6:
  • Y 71 , Y 72 , Y 73 independently from one another, denote H or F,
  • R 71 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms,
  • R 72 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms
  • X 72 denotes F, Cl; NCS or -OCF3, preferably F or NCS, and particularly preferably
  • z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula VI 1-1 are preferably selected from the group of the compounds of the formulae VI 1-1 a to VI 1-1 d:
  • R 71 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
  • 35 z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2
  • X 72 preferably denotes F. P19228 AT
  • the compounds of the formula VI 1-2 are preferably selected from the group of the compounds of the formulae VI l-2a and Vll-2b, particularly preferably of the formula VII- 2a: in which
  • R 72 has the meaning indicated above and preferably denotes C m Fh m+i
  • n and m independently of one another, denote an integer in the range from
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 71 and R 72 ) here are, in particular, (C n f i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • the compounds of the formula VII-3 are preferably compounds of the formula VI l-3a:
  • R 71 has the meaning indicated above and preferably denotes C n f i
  • the preferred combinations of (R 71 and R 72 ) here are, in particular, (Cnf i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • the compounds of the formula VII-4 are preferably compounds of the formula VI l-4a:
  • R 71 has the meaning indicated above and preferably denotes Cnf i
  • (R 71 and R 72 ) are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ) ⁇
  • the compounds of the formula VII-5 are preferably selected from the group of the compounds of the formulae VI l-5a and Vll-5b, more preferably of the formula VI l-5a:
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 71 and R 72 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • the compounds of the formula VII-6 are preferably selected from the group of the
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula VII-7 are preferably selected from the group of the compounds of the formulae VI l-7a to VI l-7d:
  • R 71 has the meaning indicated above and preferably denotes Cnf i
  • X 72 denotes F, -OCF 3 or -NCS, n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
  • 25 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula VIII are preferably selected from the group of the compounds of the formulae VIII-1 to VIII-3, more preferably these compounds of the formula VIII predominantly consist, even more preferably essentially consist and very 30 particularly preferably completely consist thereof:
  • one of Y 81 and Y 82 denotes H and the other denotes H or F, and
  • 20 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 81 and R 82 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • the compounds of the formula VI 11-1 are preferably selected from the group of the compounds of the formulae VI 11-1 a to VIIMc: VII 1-1 a
  • the preferred combinations of (R 81 and R 82 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and C m H 2m+i ).
  • the compounds of the formula VIII-2 are preferably compounds of the formula VI ll-2a: in which
  • 30 z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula VIII-3 are preferably compounds of the formula VI ll-3a: P19228 AT
  • the compounds of the formula IX are preferably selected from the group of the compounds of the formulae IX-1 to IX-3: in which the parameters have the respective meaning indicated above under formula IX
  • PCT/EP2020/085026 66 denotes
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula IX-1 are preferably selected from the group of the compounds of the formulae IX-1 a to IX-1 e: P19228 AT
  • R 91 has the meaning indicated above and preferably denotes Cnf i, and n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and
  • 10 X 92 preferably denotes F or Cl.
  • the compounds of the formula IX-2 are preferably selected from the group of the compounds of the formulae IX-2a and IX-2b: in which
  • R 92 has the meaning indicated above and preferably denotes C m H2m +i
  • n and m independently of one another, denote an integer in the range from
  • 1 to 7 preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
  • the compounds of the formula IX-3 are preferably compounds of the formulae IX-3a and IX-3b:
  • R 91 has the meaning indicated above and preferably denotes C n H 2n+i
  • the preferred combinations of (R 91 and R 92 ) here are, in particular, (C n H 2n+i and C m H 2m+i ) and (C n H 2n+i and 0-C m H 2m+i ), particularly preferably (C n H 2n+i and 0-C m H 2m+i ).
  • the medium comprises one or more compounds of formula X in which
  • R 101 denotes H, alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or
  • X 101 denotes H, F, Cl, -CN, SFs, NCS, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms,
  • Y 101 denotes methyl, ethyl or Cl, P19228 AT
  • the compounds of formula X are selected from the sub-formulae X-1 and X- 2
  • the media according to the invention comprise one or more compounds selected from the group of compounds of the formulae X-1-1 to X-1-9
  • the medium according to the invention comprises one or more compounds of formula XI in which R s denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or
  • R L on each occurrence, independently of one another, denote in which R L , on each occurrence identically or differently,
  • L S1 , L S2 identically or differently, denote H, Cl or F
  • R S1 , R S2 identically or differently, denote H, alkyl or alkenyl, having up to
  • Th1 Th2 identically or differently, denote H, alkyl or alkenyl or alkoxy, having up to 6 C atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl,
  • the compounds of formula XI are selected from the group of compounds of the formulae XI-1 to XI-24:
  • R s denotes alkyl or alkenyl having 2 to 6 C atoms, in which one or more
  • R S1 and R S2 identically or differently, denote H or alkyl having 1 to 6 C atoms, preferably H,
  • R S3 denotes H, F or alkyl, having up to 6 C atoms, or cyclopropyl, preferably
  • H F or ethyl, very preferably H
  • L S1 and L S2 identically or differently, denote H or F, preferably F.
  • the medium according to the invention comprises one or more compounds of formula T P19228 AT
  • R T denotes halogen, CN, NCS, R F , R F -0- or R F -S-, wherein
  • R F denotes fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms
  • L 4 and L 5 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms;
  • liquid crystalline media according to the invention comprise one or more compounds selected from the group of compounds of the formulae T-1a to T-3b below:
  • the media comprise one or more compounds selected from the compounds of the formulae T-1a and T-2a.
  • Preferred compounds of formula T-1a are selected from the group of compounds of the following sub-formulae:
  • n 1 , 2, 3 or 4, preferably 1.
  • Preferred compounds of formula T-2a are selected from the group of compounds of the following sub-formulae:
  • n 1 , 2, 3 or 4, preferably 1.
  • the medium according to the invention comprises one or more compounds of formula T-1a-5.
  • the media according to the present invention comprise one or more chiral dopants.
  • these chiral dopants have an absolute value of the helical twisting power (HTP) in the range of from 1 mht 1 to 150 mht 1 , preferably in the range of from 10 mht 1 to 100 mht 1 .
  • HTP helical twisting power
  • the media may comprise two or more chiral dopants, these may have opposite signs of their HTP-values. This condition is preferred for some specific embodiments, as it allows to compensate the chirality of the respective compounds to some degree and, thus, may be used to compensate various temperature dependent properties of the resulting media in the devices.
  • the chiral dopants present in the media according to the instant application are mesogenic compounds and most preferably they exhibit a mesophase on their own.
  • the medium comprises two or more chiral compounds which all have the same algebraic sign of the HTP.
  • the temperature dependence of the HTP of the individual compounds may be high or low.
  • the temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependencies of the HTP in
  • optically active component a multitude of chiral dopants, some of which are commercially available, is available to the person skilled in the art, such as, for example, cholesteryl nonanoate, R- and S-811, R- and S-1011, R- and S-2011, R- and S-3011,
  • Particularly suitable dopants are compounds which contain one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups which form a mesogenic group with the chiral group.
  • Suitable chiral groups are, for example, chiral branched hydrocarbon radicals, chiral ethane diols, binaphthols or dioxolanes, furthermore mono- or polyvalent chiral groups selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acids, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or sequences of a few, preferably 1-5, amino acids.
  • Preferred chiral groups are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols, such as, for example, sorbitol, mannitol, iditol, galactitol or anhydro derivatives thereof, in particular dianhydrohexitols, such as dianhydrosorbide (1,4:3,6-dianhydro-D-sorbide, isosorbide), dianhydromannitol
  • sugar acids such as, for example, gluconic acid, gulonic acid and ketogulonic acid
  • chiral substituted glycol radicals such as, for example, mono- or oligoethylene or propylene glycols, in which one or more CH2 groups are substituted by alkyl or alkoxy
  • amino acids such as, for example, alanine, valine, phenylglycine or phenylalanine, or sequences of from 1 to 5 of these amino
  • steroid derivatives such as, for example, cholesteryl or cholic acid radicals
  • terpene derivatives such as, for example, menthyl, neomenthyl, campheyl, pineyl, terpineyl, isolongifolyl, fenchyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.
  • the media according to the present invention preferably comprise chiral dopants which are selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in DE 3425503,
  • Chiral compounds preferably used according to the present invention are selected from the group consisting of the formulae shown below.
  • chiral dopants selected from the group consisting of compounds of the following formulae A-l to A-lll and A-Ch: in which
  • H atoms 10 and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN, preferably alkyl, more preferably n-alkyl, with the proviso that R a32 is different from R b32 ;
  • R z denotes H, CH 3 , F, Cl, or CN, preferably H or F,
  • R 8 has one of the meanings of R a11 given above, preferably alkyl, more preferably n-alkyl having 1 to 15 C atoms,
  • Z 8 denotes- C(0)0-, CH2O, CF2O or a single bond, preferably -C(0)0-,
  • a 11 is defined as A 12 below, or alternatively denotes
  • halogen CN, or alkyl, alkenyl, alkoxy or alkenyloxy having up to 12 C atoms and in which one or more H atoms are optionally replaced with halogen, preferably methyl, ethyl, Cl or F, particularly preferably F,
  • a 21 denotes
  • a 22 has the meanings given for A 12
  • a 31 has the meanings given for A 11 , or alternatively denotes
  • a 32 has the meanings given for A 12 .
  • n3 is 1, 2 or 3
  • 35 r is 0, 1, 2, 3 or 4.
  • dopants selected from the group consisting of the compounds of the following formulae: P19228 AT
  • Particularly preferred compounds of formula A are compounds of formula A- III.
  • dianhydroiditol p y ydrosorbitol
  • chiral ethane diols such as, for example, diphenylethanediol (hydrobenzoin), in particular mesogenic hydrobenzoin derivatives of the following formula A-V:
  • 30 may also be mono-, di- or trisubstituted by L, or 1 ,4-cyclo- hexylene,
  • L is H, F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms,
  • 35 c is 0 or 1 ,
  • X is CH 2 or -C(O)-, P19228 AT
  • Z° is -COO-, -OCO-, -CH2CH2- or a single bond
  • R° is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy having
  • the compounds of the formula A-IV are described in WO 98/00428.
  • the compounds of the formula A-V are described in GB-A-2, 328,207.
  • Very particularly preferred dopants are chiral binaphthyl derivatives, as described in WO 02/94805, chiral binaphthol acetal derivatives, as described in WO 02/34739, chiral TADDOL derivatives, as described in WO 02/06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group, as described in WO 02/06196 and WO 02/06195.
  • X 1 , X 2 , Y 1 and Y 2 are each, independently of one another, F, Cl, Br, I, CN, SON, SFs, straight-chain or branched alkyl having from 1 to 25 carbon atoms, which is P19228 AT
  • - 89 unsubstituted or monosubstituted or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH2 groups may each, independently of one another, be replaced by -O-, -S-, -NH-,
  • a polymerisable group or cycloalkyl or aryl having up to 20 carbon atoms which may optionally be monosubstituted or polysubstituted by halogen, preferably F, or by a polymerisable group
  • x 1 and x 2 are each, independently of one another, 0, 1 or 2
  • y 1 and y 2 are each, independently of one another, 0, 1, 2, 3 or 4
  • B 1 and B 2 are each, independently of one another, an aromatic or partially or fully saturated aliphatic six-membered ring in which one or more CH groups may each be replaced by N and one or more non-adjacent CH2 groups may each be replaced by O or S,
  • W 1 and W 2 are each, independently of one another, -Z 1 -A 1 -(Z 2 -A 2 ) m -R, and one of the two is alternatively R 1 or A 3 , but both are not simultaneously H, or
  • U 1 and U 2 are each, independently of one another, CH2, O, S, CO or CS, V 1 and V 2 are each, independently of one another, (CH2) n , in which from one to four non-adjacent CH2 groups may each be replaced by O or S, and one of V 1 and V 2 and, in the case where
  • n 1 ,2 or 3
  • Z 1 and Z 2 are each, independently of one another, -O-, -S-, -CO-, -COO-, -OCO-, -O- 35 COO-, -CO-NR x -, -NR x -CO-, -O-CH2-, -CH2-O-,
  • R x denotes alkyl having 1 to 6 C atoms
  • a 1 , A 2 and A 3 are each, independently of one another, 1,4-phenylene, in which one or two non-adjacent CH groups may each be replaced by N, 1,4- cyclohexylene, in which one or two non-adjacent CH2 groups may each be replaced by O or S, 1,3-dioxolane-4,5-diyl, 1 ,4-cyclohexenylene, 1,4- bicyclo[2.2.2]octylene, piperidine-1 ,4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2,6-diyl or 1 ,2,3,4-tetrahydronaphthalene-2,6-diyl, where each of these groups may be monosubstituted or polysubstituted by L, and in addition A 1 can be a single bond,
  • L is a halogen atom, preferably F, CN, NO 2 , alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms, in which one or more H atoms may each be replaced by F or Cl, m is in each case, independently, 0, 1 , 2 or 3, and
  • the concentration of the one or more chiral dopant(s), in the LC medium is preferably in the range from 0.001 % to 20 %, preferably from 0.05 % to 5 %, more preferably from 0.1 % to 2 %, and, most preferably from 0.5 % to 1.5 %.
  • concentration ranges apply in particular to the chiral dopant S-4011 or R-4011 (both from Merck KGaA) and for chiral dopants having the same or a similar HTP.
  • S-4011 or R-4011 both from Merck KGaA
  • these preferred concentrations have to be decreased, respectively increased proportionally according to the ratio of their HTP values relatively to that of S-4011.
  • the pitch p of the LC media or host mixtures according to the invention is preferably in
  • the media according to the invention comprise a stabilizer selected from the group of compounds of the formulae ST-1 to ST-18. P19228 AT
  • R ST denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by -CoC-, -CF2O-, -OCF2-,
  • U and L 2 each, independently of one another, denote F, Cl, CF 3 or CHF 2 , P denotes 1 or 2, and
  • n preferably denotes 3.
  • n preferably denotes 7.
  • Very particularly preferred mixtures according to the invention comprise one or more 5 stabilizers from the group of the compounds of the formulae ST-2a-1 , ST-3a-1 , ST-3b-1, ST-8-1, ST-9-1 and ST-12: P19228 AT
  • the compounds of the formulae ST-1 to ST-18 are preferably each present in the liquid-crystal mixtures according to the invention in amounts of 0.005 - 0.5%, based on the mixture.
  • the concentration correspondingly increases to 0.01 - 1% in the case of two compounds, based on the mixtures.
  • the total proportion of the compounds of the formulae ST-1 to ST-18, based on the mixture according to the invention, should not exceed 2%.
  • the total concentration of compounds of formula C in the liquid-crystalline medium is 5 % or more, preferably 8 % or more, very preferably 10% or more and particularly preferably 12 % or more.
  • the liquid-crystalline media preferably comprise in total 2 % to 40 %, preferably 5 % to 30 % and particularly preferably 8 % to 25 % of compounds of formula C.
  • the liquid-crystalline media comprise in total 5 % to 45 %, preferably 10 % to 40 % and particularly preferably 21/116080 PCT/EP2020/085026
  • the liquid-crystalline media comprise in total 5 % to 35 %, preferably 10 % to 30 % and particularly preferably 15 % to 25 % of one or more compounds of the formula T-1a.
  • the liquid-crystalline media comprise in total 5 % to 35 %, preferably 10 % to 30 % and particularly preferably 15 % to 25 % of one or more compounds of the formula T-1a, and in addition 5 to 15% of one or more compounds of the formula T-2a-4.
  • the medium comprises one or more compounds of formula I, preferably of formula I-2 or I-3, in a total concentration in the range of from 1 % to 25 %, more preferably from 2 % to 20 %, and particularly preferably from 5 % to 15 %.
  • the medium comprises one or more compounds of formula II, preferably of formula 11-1, in a total concentration of 5 % to 35 %, more preferably 10 % to 30 %, particularly preferably 15 % to 25 %.
  • the medium comprises one or more compounds of formula IIA-1 in a total concentration of 5 % to 25 %, more preferably 8 % to 20 %, particularly preferably 12 % to 17 %.
  • the medium comprises one or more compounds of formula 11-1 in an total concentration of 30% or less, more preferably 25% or less, particularly preferably 20% or less.
  • the medium comprises one or more compounds of formula III, preferably ill-1 and/or ill-2, more preferably 111-1 h and/or Ill- lb, in a total concentration of 15 % to 70 %, more preferably 25 % to 60 %, particularly preferably 35 % to 50 %.
  • the medium comprises one or more compounds of the formulae C and I and II and/or IIA, and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more.
  • the medium comprises one or more compounds of the formulae C and II and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more.
  • the medium comprises one or more compounds of the formulae C and I and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more.
  • the medium comprises one, two, three, four or more compounds of formula 111-1 ,
  • the medium comprises a compound of formula 111- 1b, preferably in a total concentration in the range of from 5% to 35%, more preferably 10% to 30%, in particular 15% to 25%;
  • the medium comprises a compound of formula lll-1h, preferably in a total concentration in the range of from 10% to 40%, more preferably 15% to 35%, in particular 18% to 30%;
  • the medium comprises the compound PPU-TO-S and/or PPTU-TO-S and/or PTPU-TO-S and/or PP(1)TO-n-S;
  • the medium comprises one or more compounds of formula l-2d, preferably the compounds PGU-2-S and/or PGU-3-S and/or PGU-4-S, and/or CPU-2-S and/or CPU-3-S and/or CPU-4-S;
  • the medium comprises one or more compounds of formula l-2d and formula 11-1 b, preferably the compounds PGU-3-S and/or PGU-4-S and PTU-3-S and/or PTU-4-S
  • the medium comprises one or more compounds of formula PPTU-n-S and/or PTPU-n-S in an total concentration in the range of from 15 to 25 %;
  • the medium comprises one or more compounds of formula PPTU-n-S and/or PTPU-n-S and/or PGTU-n-S in a total concentration in the range of from 15 to
  • n 1 , 2, 3, 4, 5, or 6; P19228 AT
  • the medium comprises one or more compounds of formula ST-3, preferably ST-3a and/or ST-3b, particularly preferably ST-3b-1, in a total concentration in the range of from 0.01 to 1%, preferably from 0.05 to 0.5%, particularly from 0.10 to 0.15%.
  • the liquid-crystal media in accordance with the present invention preferably have a clearing point of 90°C or more, more preferably 100°C or more, more preferably 110°C or more, more preferably 120°C or more, more preferably 130°C or more, particularly preferably 140°C or more and very particularly preferably 150°C or more.
  • the liquid-crystal media in accordance with the present invention preferably have a clearing point of 160°C or less, more preferably 140°C or less, particularly preferably 120°C or less, and very particularly preferably 100°C or less.
  • the nematic phase of the media according to the invention preferably extends at least from 0°C or less to 90°C or more. It is advantageous for the media according to the invention to exhibit even broader nematic phase ranges, preferably at least from -10°C or less to 120°C or more, very preferably at least from -20°C or less to 140°C or more and in particular at least from -30°C or less to 150°C or more, very particularly preferably at least from -40°C or less to 170°C or more.
  • the De of the liquid-crystal medium according to the present invention is preferably 5 or more, more preferably 7 or more and very preferably 10 or more.
  • the birefringence (Dh) of the liquid-crystal media according to the present invention is preferably 0.280 or more, more preferably 0.300 or more, even more preferably 0.320 or more, very preferably 0.330 or more and in particular 0.350 or more.
  • the Dh of the liquid-crystal media according to the present invention is preferably in the range from 0.200 to 0.900, more preferably in the range from 0.250 to 0.800, even more preferably in the range from 0.300 to 0.700 and very particularly preferably in the range from 0.350 to 0.600.
  • the Dh of the liquid-crystal media in accordance with the present invention is preferably 0.50 or more, more preferably 0.55 or more.
  • the compounds of the formulae I to III in each case include dielectrically positive compounds having a dielectric anisotropy of greater than 3, dielectrically neutral compounds having a dielectric anisotropy of less than 3 and greater than -1.5 and dielectrically negative compounds having a dielectric anisotropy of -1.5 or less.
  • the compounds of the formulae C, I, II and III are preferably dielectrically positive.
  • dielectrically positive describes compounds or components where De > 3.0
  • dielectrically neutral describes those where -1.5 ⁇ De ⁇ 3.0
  • dielectrically negative describes those where De ⁇ -1.5.
  • De is determined at a frequency of 1 kHz and at 20°C.
  • the dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10 %, the concentration is reduced to 5 %.
  • the capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 pm.
  • the voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.
  • De is defined as (e 1 1 - e ⁇ ), while e 3nq. is (e 1 1 + 2 e ⁇ ) / 3.
  • the host mixture used for the determination of physical constants of pure compounds by extrapolation is ZLI-4792 from Merck KGaA, Germany.
  • the absolute values of the dielectric constants, the birefringence (Dh) and the rotational viscosity (gi) of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds.
  • the concentration in the host is 10 % or in case of insufficient solubility 5 %.
  • the values are extrapolated to a concentration of 100 % of the added compounds.
  • phase sequences of pure compounds are given using the following abbreviations: 21/116080 PCT/EP2020/085026
  • K crystalline
  • N nematic
  • SmA smectic A
  • SmB smectic B
  • I isotropic.
  • Components having a nematic phase at the measurement temperature of 20°C are measured as such, all others are treated like compounds.
  • the expression threshold voltage in the present application refers to the optical threshold and is quoted for 10 % relative contrast (Vio), and the expression saturation voltage refers to the optical saturation and is quoted for 90 % relative contrast (Vgo), in both cases unless expressly stated otherwise.
  • the capacitive threshold voltage (Vo), also called the Freedericks threshold (V Fr ), is only used if expressly mentioned.
  • the threshold voltages are determined using test cells produced at Merck KGaA, Germany.
  • the test cells for the determination of De have a cell thickness of approximately 20 pm.
  • the electrode is a circular ITO electrode having an area of 1.13 cm 2 and a guard ring.
  • the orientation layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic orientation (e
  • the capacitances are determined using a Solatron 1260 frequency response analyser using a sine wave with a voltage of 0.3 V rms .
  • the light used in the electro-optical measurements is white light.
  • V50 mid-grey
  • V90 saturation
  • the liquid-crystalline media are investigated with respect to their properties in the microwave frequency range as described in A. Penirschke et al. “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz”, 34 th European Microwave Conference - Amsterdam, pp. 545-548. Compare in this respect also A. Gaebler et al. “Direct Simulation of Material Permittivities ", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, and DE 102004029429 A, in which a measurement method is likewise described in detail.
  • the liquid crystal is introduced into a polytetrafluoroethylene (PTFE) or quartz capillary.
  • the capillary has an inner diameter of 0.5mm and an outer diameter of 0.78mm.
  • the effective length is 2.0 cm.
  • the filled capillary is introduced into the center of the cylindrical cavity with a resonance frequency of 19 GHz.
  • This cavity has a length of 11.5 mm and a radius of 6 mm.
  • the input signal (source) is then applied, and the frequency depending response of the cavity is recorded using a commercial vector network analyzer (N5227A PNA Microwave Network Analyzer, Keysight Technologies Inc. USA. For other frequencies, the dimensions of the cavity are adapted correspond ingly.
  • the values for the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by alignment of the liquid crystal in a magnetic field.
  • the magnetic field of a permanent magnet is used.
  • the strength of the magnetic field is 0.35 tesla.
  • Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuit adaptive filters and others. 21/116080 PCT/EP2020/085026
  • All mixtures according to the invention are nematic.
  • the liquid-crystal media according to the invention preferably have nematic phases in preferred ranges given above.
  • the expression have a nematic phase here means on the one hand that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating from the nematic phase.
  • the clearing point is measured in capillaries by con ventional methods.
  • the investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage of bulk samples:
  • the storage stability in the bulk (LTS) of the media according to the invention at a given temperature T is determined by visual inspection.
  • 2 g of the media of interest are filled into a closed glass vessel (bottle) of appropriate size placed in a refrigerator at a predetermined temperature.
  • the bottles are checked at defined time intervals for the occurrence of smectic phases or crystallization. For every material and at each temperature two bottles are stored. If crystallization or the appearance of a smectic phase is observed in at least one of the two correspondent bottles the test is terminated and the time of the last inspection before the one at which the occurrence of a higher ordered phase is observed is recorded as the respective storage stability.
  • the test is finally terminated after 1000 h, i.e an LTS value of 1000 h means that the mixture is stable at the given temperature for at least 1000 h.
  • the liquid crystals employed preferably have a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more and very particularly preferably 10 or more.
  • the liquid-crystal media according to the invention are characterized by high anisotropy values in the microwave range.
  • the birefringence at about 19 GHz is, for example, preferably 0.14 or more, particularly preferably 0.15 or more, particularly preferably 0.20 or more, particularly preferably 0.25 or more and very particularly preferably 0.30 or more.
  • the birefringence is preferably 0.80 or less.
  • the dielectric anisotropy in the microwave range is defined as 21/116080 PCT/EP2020/085026
  • the tunability (t) is defined as
  • the material quality (h) is defined as h o (t / tan d e r, max ), where the maximum dielectric loss is tan de r,max. o max. ⁇ tan d e r , ⁇ tan d e r , 1 1 ⁇ .
  • the tunability t of the medium according to the invention, measured at 20°C and 19 GHz is 0.250 or more, preferably 0.300 or more, 0.310 or more, 0.320 or more, 0.330 or more, or 0.340 or more, very preferably 0.345 or more and in particular 0.350 or more.
  • the material quality (h) of the preferred liquid-crystal materials is 6 or more, preferably 8 or more, preferably 10 or more, preferably 15 or more, preferably 17 or more, preferably 20 or more, particularly preferably 25 or more and very particularly preferably 30 or more.
  • the preferred liquid-crystal materials have phase shifter qualities of 15 dB or more, preferably 207dB or more, preferably 307dB or more, preferably 407dB or more, preferably 507dB or more, particularly preferably 807dB or more and very particularly preferably 1007dB or more.
  • liquid crystals having a negative value of the dielectric anisotropy can also advantageously be used.
  • the liquid crystals employed are either individual substances or mixtures. They preferably have a nematic phase.
  • the liquid-crystal media in accordance with the present invention may comprise further additives and chiral dopants in the usual concentrations.
  • the media according to the present invention comprise one or more chiral compounds as chiral dopants in order to adjust their cholesteric pitch.
  • Their total concentration in the media according to the instant invention is preferably in the range 0.05 % to 15 %, more preferably from 1 % to 10 % and most preferably from 2 % to 6 %.
  • the media according to the present invention may comprise further liquid crystal compounds in order to adjust the physical properties.
  • Such compounds are known to the skilled person.
  • Their concentration in the media according to the instant invention is preferably 0 % to 30 %, more preferably 0.1 % to 20 % and most preferably 1 % to 15 %.
  • the liquid-crystal media according to the invention consist of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20 and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the dissolution process. It is, however, also possible to prepare the media in other conventional ways, for example using so-called pre-mixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called “multi-bottle” systems, the constituents of which are themselves ready-to-use mixtures. P19228 AT
  • CH denote straight-chain alkyl or alkylene, respectively, in each case having n, m or I C atoms, wherein n and m, independently are 1, 2, 3, 4, 5, 6 or 7 and I is 1 , 2 or 3.
  • Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups.
  • Table C gives the meanings of 15 the codes for the left-hand or right-hand end groups.
  • Table D shows illustrative structures of compounds with their respective abbreviations.
  • V -CH CH- Zl -O-CO-
  • n identically or differnetly, are 1,2, 3, 4, 5, 6 or 7.
  • the medium according to the invention comrises one or more compounds selected from the compounds of Table C.
  • Table D shows illustrative compounds which can be used as alternative stabilizers in the mesogenic media in accordance with the present invention.
  • the total concentration of these and similar compounds in the media is preferably 5 % or less.
  • the mesogenic media comprise one or more compounds selected from the group of the compounds from Table D.
  • Table E shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media in accordance with the present invention.
  • the mesogenic media comprise one or more compounds selected from the group of the compounds of Table E.
  • the mesogenic media in accordance with the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.
  • RT room temperature typically 20°C ⁇ 1°C

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Abstract

The present invention relates to aromatic isothiocyanates of formula C (C) as defined in claim 1, to liquid-crystalline media comprising one or more compounds of formula C and to high-frequency components comprising these media, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas, e.g. phased array antennas.

Description

P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 1 -
Aromatic Isothiocyanates
The present invention relates to aromatic isothiocyanates, liquid-crystalline media comprising same, and to high-frequency components comprising these media, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas (e.g. phased array antennas), and to devices comprising said components.
Liquid-crystalline media have a been used for many years in electro-optical displays (liquid crystal displays: LCDs) in order to display information. More recently, however, liquid-crystalline media have also been proposed for use in components for microwave technology, such as, for example, in DE 102004029429.1 A and in JP 2005- 120208 (A).
A. Gaebler, F. Goelden, S. Muller, A. Penirschke and R. Jakoby “Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formulation of the Vector Variational Approach”, 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, describe the corresponding properties of the known liquid-crystal mixture E7 (Merck KGaA, Germany).
DE 102004029429 A describes the use of liquid-crystal media in microwave technology, inter alia in phase shifters. Therein, liquid-crystalline media with respect to their properties in the corresponding frequency range have been discussed and liquid- crystalline media based on mixtures of mostly aromatic nitriles and isothiocyanates have been shown.
Fluorine atoms are commonly used in mesogenic compounds to introduce polarity. Especially in combination with a terminal NCS group high dielectric anisotropy values can be achieved.
In EP 2 982 730 A1, mixtures are described that completely consist of isothiocyanate compounds.
35 P19228 AT
WO 2021/116080 PCT/EP2020/085026 2
However, compositions available for the use in microwave applications are still afflicted with several disadvantages. It is required to improve these media with respect to their general physical properties, the shelf life and the stability under operation in a device.
In view of the multitude of different parameters which have to be considered and improved for the development of liquid crystalline media for microwave application it is desirable to have a broader range of possible mixture components for the development of such liquid-crystalline media.
An object of the present invention is to provide a compound for the use in liquid crystalline media with improved properties relevant for the application in the microwave range of the electromagnetic spectrum.
To solve the problem, a compound of formula C shown below is provided and a liquid crystalline medium comprising the compound.
15
The present invention relates to a compound of formula C
20 in which
Rc denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more Chh-groups may
25 be replaced group Rp,
Rp denotes halogen, CN, NCS, RF, RF-0- or RF-S-, wherein
RF denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms,
30 ZC1, ZC2 identically or differently, denote -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -CºC- or a single bond, preferably -CºC- or a single bond,
X denotes Cl or F, preferably F,
Y denotes H, Cl, F, alkyl or alkoxy each having 1 to 6 C atoms, preferably, H, F,
35 CH3 or C2H5, very preferably H, t is 0, 1 or 2, preferably 0 or 1, and P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 3 - and \ — t denote a radical selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-
5 naphthylene, in which one or two CH groups may be replaced by N and in which one or more H atoms may be replaced by L, b) the group consisting of trans-1, 4-cyclohexylene, 1 ,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, in which one
10 or more non-adjacent CH2 groups may be replaced by -O- and/or -S- and in which one or more H atoms may be replaced by F, c) the group consisting of thiophene-2, 5-diyl, thieno[3,2-b]thiophene-2,5- diyl, selenophene-2, 5-diyl, each of which may also be mono- or polysubstituted by L, wherein
15 L on each occurrence, identically or differently, denotes F, Cl, CN,
SCN, SF5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkyl- carbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms.
20 The present invention further relates to a compound of formula N
25 in which the occurring groups and parameters have the meanings given above for formula C.
According to another aspect of the present invention there is provided a process for the synthesis of compounds of formula C from compounds of formula N.
30
The present invention further relates to a liquid-crystalline medium comprising a compound of formula C and to the use of a liquid-crystalline medium comprising a compound of formula C in a component for high-frequency technology.
35 According to another aspect of the present invention there is provided a component and a device comprising said component, both operable in the microwave region of the 21/116080 PCT/EP2020/085026
- 4 - electromagnetic spectrum. Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuits and adaptive filters.
Preferred embodiments of the present invention are subject-matter of the dependent claims or can also be taken from the description.
Surprisingly, it has been found that it is possible to achieve liquid-crystalline media having excellent stability and at the same time a high dielectric anisotropy, suitably fast switching times, a suitable, nematic phase range, high tunability and low dielectric loss, by using compounds of formula C in liquid-crystalline media.
The media according to the present invention are distinguished by a high clearing temperature, a broad nematic phase range and excellent low-temperature stability (LTS). As a result, devices containing the media are operable under extreme temperature conditions.
The media are further distinguished by high values of the dielectric anisotropy and low rotational viscosities. As a result, the threshold voltage, i.e. the minimum voltage at which a device is switchable, is very low. A low operating voltage and low threshold voltage is desired in order to enable a device having improved switching characteristics and high energy efficiency. Low rotational viscosities enable fast switching of the devices according to the invention.
These properties as a whole make the media particularly suitable for use in components and devices for high-frequency technology and applications in the microwave range, in particular devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas (e.g. phased array antennas).
Herein, “high-frequency technology” means applications of electromagnetic radiation having frequencies in the range of from 1 MHz to 1 THz, preferably from 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, particularly preferably from about 5 GHz to 150 GHz.
As used herein, halogen is F, Cl, Br or I, preferably F or Cl, particularly preferably F. P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 5 -
Herein, alkyl is straight-chain or branched and has 1 to 15 C atoms, is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.
5 Herein, branched alkyl is preferably isopropyl, s-butyl, isobutyl, isopentyl, 2- methylbutyl, 2-methylhexyl or 2-ethylhexyl.
Herein, an alkoxy radical is straight-chain or branched and contains 1 to 15 C atoms. It is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C
10 atoms and is accordingly preferably methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy or n-heptoxy.
Herein, an alkenyl radical is preferably an alkenyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one C-C double bond. It is
15 preferably straight-chain and has 2 to 7 C atoms. Accordingly, it is preferably vinyl, prop-1- or -2-enyl, but-1 -, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl. If the two C atoms of the C-C double bond are substituted, the alkenyl radical can be in the form of E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred. Of the alkenyl radicals,
20 prop-2-enyl, but-2- and -3-enyl, and pent-3- and -4-enyl are particularly preferred.
Herein, alkynyl is taken to mean an alkynyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one C-C triple bond. 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.
25
In case RF denotes a halogenated alkyl-, alkoxy-, alkenyl or alkenyloxy it can be branched or unbranched. Preferably it is unbranched, mono- poly or perfluorinated, preferably perfluorinated and has 1, 2, 3, 4, 5, 6 or 7 C atoms, in case of alkenyl 2, 3, 4, 5, 6 or 7 C atoms.
30
Rp preferably denotes CN, NCS, Cl, F, -(CH2)n-CH=CF2, -(CH2)n-CH=CHF, -(CH2)n- CH=CI2, -CnF2n+i, -(CF2)n-CF2H, -(CH2)n-CF3, -(CH2)n-CHF2, -(CH2)nCH2F, -CH=CF2, - 0(CH2)n-CH=CF2, -0(CH2)nCHCI2, -OCnF2n+1, -0(CF2)n-CF2H, -0(CH2)nCF3, -0(CH2)n- CHF2, -0(CF)nCH2F, -OCF=CF2, -SCnF2n+i, -S(CF)n-CF3, wherein n is an integer from 0
35 to 7. 21/116080 PCT/EP2020/085026 6
The compounds of the general formula C are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme- Verlag, Stuttgart), to be precise under reaction conditions which are known and are suitable for said reactions. Use can be made here of variants which are known per se, but are not mentioned here in greater detail.
If desired, the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead by immediately reacting them further into the compounds of the general formula C.
Preferred synthetic pathways towards compounds according to the invention are exemplified in the schemes below, and are further illustrated by means of the working examples. Suitable syntheses are also published for example in Juanli Li, Jian Li, Minggang Hu, Zhaoyi Che, Lingchao Mo, Xiaozhe Yang, Zhongwei An & Lu Zhang (2017) The effect of locations of triple bond at terphenyl skeleton on the properties of isothiocyanate liquid crystals, Liquid Crystals, 44:9, 1374-1383 and can be adapted to the particular desired compounds of the general formula C by choice of suitable starting materials.
Preferred intermediates are 4-bromo-2,6-dichloroaniline and 4-bromo-2-chloro-6- fluoroaniline, both described in the literature, which can be reacted to give compounds of the formula N for example by cross coupling reactions commonly known as Suzuki, Stille, Sonogashira reactions, and the like. Preferred pathways are exemplified in schemes 1 and 2, in which the groups and parameters have the meanings defined in claim 1. P19228 AT
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- 7 -
Scheme 1
Scheme 2
Preferred reagents for the process according to the invention for the transformation of compounds of the formula N into compounds of the formula C (scheme 3) are carbon disulfide, thiophosgene, thiocarbonyl diimidazole, di-2-pyridyl thionocarbonate, bis(dimethylthiocarbamoyl) disulfide, dimethylthiocarbamoyl chloride and phenyl chlorothionoformate, very preferably thiophosgene.
20
Scheme 3
The reactions described should only be regarded as illustrative. The person skilled in
30 the art can carry out corresponding variations of the syntheses described and also follow other suitable synthetic routes in order to obtain compounds of the formula C.
According to a first aspect of the present invention there are provided compounds of formula C in which Rc denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl,
35 alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CH2-groups P19228 AT
WO 2021/116080 PCT/EP2020/085026 8 may be replaced preferably alkyl having 1 to 12 C atoms.
According to a second aspect of the present invention there are provided compounds of formula C in which the group Rc denotes Rp, where Rp denotes halogen, CN, NCS, RF, RF-0- or RF-S-, and wherein RF denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms, preferably CF3 or OCF3. f formula C are preferably selected from the compounds in which the
L1 and L2 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms, and where the other groups and parameters have the meanings given above.
35 In a preferred embodiment of the present invention, the compounds of formula C are selected from the compounds of the formulae C-1 to C-11 : PCT/EP2020/085026 P19228 AT
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- IQ -
10
15 L1, L2 and L3 identically or differently, denote H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and
Rc and X have the meanings given above and preferably Rc denotes alkyl having 1 to 7 C atoms or a group Rp,
20 where Rp preferably denotes perfluorinated alkoxy having 1 to 7 C atoms, and X denotes F.
Preferably, one of the groups ZC1 and ZC2 of formula C denotes a single bond and the other one of ZC1 and ZC2 denotes -CºC-.
Very preferred compounds of the formula C are selected from the compounds of the following sub-formulae: P19228 AT
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- 11 P19228 AT
WO 2021/116080 PCT/EP2020/085026 12 P19228 AT
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- 13 - in which Rc has the meanings given above and preferably denotes alkyl having 1 to 7 C atoms or CF3O.
Very particularly preferred compounds are the compounds of the formulae C-7-1, C-9- 1, C-9-4, C-10-1, C-10-2, C-10-3, C-10-4, C-10-5, C-10-6, and C-10-7.
In a preferred embodiment of the present invention the medium comprises one or more compounds selected from the group of compounds of the formulae I, II and III,
10
15 in which R1 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluorinated
20 alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, in which one or more Chh-groups may be replaced by preferably unfluorinated alkyl or unfluorinated alkenyl,
25 n is 0, 1 or 2, to on each occurrence, independently of one another, denote
30
35 P19228 AT
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- 14 - in which RL , on each occurrence, identically or
10 differently, denotes H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H, and wherein and in case n = 2, one of preferably denotes and the other preferably denotes P19228 AT
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- 15 - preferably ly denotes
R2 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluori
30 nated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, in which one or more Chh-groups may
35 preferably unfluorinated alkyl or unfluorinated alkenyl, P19228 AT
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- 16 - preferably -CºC- independently of one another, denote
20 in which RL, on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H, and wherein
25 preferably
30 independently of one another, denote P19228 AT
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- 17 -
10 preferably denotes more preferably
20
25
R3 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or unfluorinated alkenyl, unfluori nated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, in which one or more CFh-groups may
30 be replaced preferably unfluorinated alkyl or unfluorinated alkenyl,
35 one of Z31 and Z32 , preferably Z32; denotes trans- CH=CH-, frans-CF=CF- or -CºC- and the other one, independently thereof, denotes -CºC-, trans- CH=CH-, frans-CF=CF- or a single bond, preferably one of them, P19228 AT
WO 2021/116080 PCT/EP2020/085026 18 preferably Z32; denotes -CºC- or trans- CH=CH- and the other denotes a single bond, and independently of one another, denote
20 in which RL , on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, particularly preferably H, and wherein
25
30 preferably
35 independently of one another, denote PI 9228 AT
WO 2021/116080 PCT/EP2020/085026 19 5
In the compounds of the formulae I, II and III, RL preferably denotes H. P19228 AT
WO 2021/116080 PCT/EP2020/085026 20
In another preferred embodiment, in the compounds of formulae I, II and III, one or two groups RL , preferably one group RL is different from H. ln a preferred embodiment of the present invention, the compounds of formula I are selected from the group of compounds of the formulae 1-1 to I-5: in which
L1, L2 and L3 on each occurrence, identically or differently, denote H or F, and the other groups have the respective meanings indicated above for formula I and preferably
R1 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
The media preferably comprise one or more compounds of formula 1-1 , which are preferably selected from the group of the compounds of the formulae 1-1 a to 1-1 d, preferably of formula 1-1 b: P19228 AT
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- 21
15 in which R1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
The media preferably comprise one or more compounds of formula I-2, which are preferably selected from the group of the compounds of the formulae l-2a to l-2e, preferably of formula l-2c:
35 P19228 AT
WO 2021/116080 PCT/EP2020/085026 22 in which R1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
The media preferably comprise one or more compounds of formula I-3, which are preferably selected from the group of the compounds of the formulae l-3a to l-3d , particularly preferably of formula l-3b: in which R1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
35 P19228 AT
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- 23 -
The media preferably comprise one or more compounds of formula I-4, which are preferably selected from the group of the compounds of the formulae l-4a to l-4e, particularly preferably of formula l-4b: in which R1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C
25 atoms.
The media preferably comprise one or more compounds of formula I-5, which are preferably selected from the group of the compounds of the formulae l-5a to l-5d, particularly preferably of formula l-5b:
35 P19228 AT
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- 24 - in which R1 has the meaning indicated above for formula I and preferably denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms.
15
The media preferably comprise one or more compounds of formula II, which are preferably selected from the group of the compounds of the formulae 11-1 to II-3, preferably selected from the group of the compounds of the formulae 11-1 and II-2:
20 11-1
25
30 in which the occurring groups have the meanings given under formula II above and preferably
R2 denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or
35 unfluorinated alkenyl having 2 to 7 C atoms, and one of P19228 AT
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- 25 - and the other, independently denotes
20 preferably
25 most preferably and preferably
R2 denotes Cnf i or CH2=CH-(CH2)z, and
30 n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
35 P19228 AT
WO 2021/116080 PCT/EP2020/085026 26
The compounds of formula 11-1 are preferably selected from the group of the compounds of the formulae 11-1 a to 11-1 e: in which
25
R2 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and n independently of one another, denote an integer in the range from
30 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
35
The compounds of formula II-2 are preferably selected from the group of the compounds of the formulae ll-2a and ll-2b: P19228 AT
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- 27 -
10
R2 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and
15 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The compounds of formula II-3 are preferably selected from the group of the compounds of the of formulae ll-3a to ll-3d:
35 P19228 AT
WO 2021/116080 PCT/EP2020/085026 28
5 in which R2 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and
10 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The compounds of formula III are preferably selected from the group of the compounds of the formulae II 1-1 to NI-6, more preferably of the formulae selected from the group of the compounds of the formulae NI-1, NI-2, NI-3 and NI-4, and particularly preferably of in which
Z31 and Z32 independently of one another denote frans-CH=CH- or trans-
CF=CF-, preferably frans-CH=CH-, and in formula NI-6
35 alternatively one of Z31 and Z32 may denote -CºC- and the other groups have the meaning given above under formula III, P19228 AT
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- 29 - and preferably R3 denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms, and one of
5 to , , denotes
30
35 P19228 AT
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- 30 -
10 where
15 and preferably
R3 denotes Cnf i or CH2=CH-(CH2)z, n denotes an integer in the range from 0 to 15, preferably in the
20 range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The compounds of formula 111-1 are preferably selected from the group of the 25 compounds of the formulae II 1-1 a to 111-1 k, more preferably selected from the group of the compounds of the formulae lll-1a, 111-1 b, 111-1 g and lll-1h, particularly preferably of formula 111-1 b and/or lll-1h: P19228 AT
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- 32 - in which R3 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The compounds of formula III-2 are preferably compounds of formula lll-2a to III-2I, very preferably II l-2b and/or 111 -2j :
10 P19228 AT
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- 33 -
R3 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z,
25 n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The compounds of formula 111-5 are preferably selected from the compounds of formula P19228 AT
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- 34 -
R3 has the meaning indicated above for formula III-5 and preferably denotes Cnf i, in which n denotes an integer in the range from 0 to 7, preferably in the range from 1 to 5.
In a preferred embodiment, the media according to the invention comprise one or more compounds selected from the group of compounds of the formulae IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2:
10
15
20
25
30 P19228 AT
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- 35 - R1 denotes alkyl or alkenyl having up to 7 C atoms, preferably ethyl, n-propyl, n- butyl or n-pentyl, n-hexyl,
RL on each occurrence, the same or differently, denotes alkyl or alkenyl having 1 to 5 C atoms, or cycloalkyl or cycloalkenyl each having 3 to 6 C atoms, preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl, very preferably ethyl, P19228 AT
WO 2021/116080 PCT/EP2020/085026 36 and from which the compounds of formula 11-1 are excluded.
Additionally, the liquid-crystalline media according to the present invention in a certain embodiment, which may be the same or different from the previous preferred embodiments preferably comprise one or more compounds of formula IV, IV in which
10 preferably
20
35 particularly preferably P19228 AT
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- 37 -
L4 denotes H or alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6
C atoms or cycloalkenyl having 4 to 6 C atoms, preferably CH3, C2H5, A7-C3H7, /-C3H7, cyclopropyl, cyclobutyl, cyclohexyl, cyclopent-1-enyl or cyclohex- 1-enyl, and particularly preferably CH3, C2H5, cyclopropyl or cyclobutyl, denotes H, alkyl having 1 to 3 C atoms or halogen, preferably H, F or Cl, more preferably H or F and very particularly preferably F,
R41 to R44, independently of one another, denote unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 15 C atoms, unfluorinated
20 alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl, each having up to 15 C atoms, and alternatively one of R43 and R44 or both also denote H, preferably R41 and R42, independently of one another, denote unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each
30 having 2 to 7 C atoms, particularly preferably
R41 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each having 2 to 7 C atoms, and particularly preferably P19228 AT
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- 38 -
R42 denotes unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 7 C atoms, and preferably
5 R43 and R44 denote H, unfluorinated alkyl having 1 to 5 C atoms, unfluorinated cycloalkyl or cycloalkenyl having 3 to 7 C atoms, unfluorinated alkylcyclohexyl or unfluorinated cyclohexylalkyl, each having 4 to 12 C atoms, or unfluorinated alkylcyclohexylalkyl having 5 to 15 C atoms, particularly preferably cyclopropyl, cyclobutyl or cyclohexyl,
10 and very particularly preferably at least one of R43 and R44 denotes n-alkyl, particularly preferably methyl, ethyl or n-propyl, and the other denotes H or n-alkyl, particularly preferably H, methyl, ethyl or n-propyl.
15 in a preferred embodiment of the present invention, the liquid-crystal medium additionally comprises one or more compounds selected from the group of compounds of the formulae V, VI, VII, VIII and IX: in which
L51 denotes R51 or X51 ,
L52 denotes R52 or X52,
R51 and R52, independently of one another, denote H, unfluorinated alkyl or
35 unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated P19228 AT
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- 39 - alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated alkenyl,
X51 and X52, independently of one another, denote H, F, Cl, -CN, SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and independently of one another, denote preferably
25
30
L61 denotes R61 and, in the case where Z61 and/or Z62 denote trans- CH=CH- or frans-CF=CF-, alternatively also denotes X61,
L62 denotes R62 and, in the case where Z61 and/or Z62 denote trans-
35 CH=CH- or frans-CF=CF-, alternatively also denotes X62,
R61 and R62, independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or P19228 AT
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- 40 - unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated alkenyl,
X61 and X62, independently of one another, denote F or Cl, -CN, SFs, fluorinated alkyl or alkoxy having 1 to 7 C atoms or fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms, one of
Z61 and Z62 denotes frans-CH=CH-, frans-CF=CF- or -CºC- and the other, independently thereof, denotes frans-CH=CH-, frans-CF=CF- or a single bond, preferably one of them denotes -CºC- or trans- CH=CH- and the other denotes a single bond, and independently of one another, denote P19228 AT
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- 41 - and x denotes 0 or 1;
L71 denotes R71 or X71 ,
5 |_72 denotes R72 or X72,
R71 and R72, independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably
10 alkyl or unfluorinated alkenyl,
X71 and X72, independently of one another, denote H, F, Cl, -CN, -NCS, -SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated or fluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms,
15 preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and
Z71 to Z73, independently of one another, denote trans- CH=CH-, trans- CF=CF-, -CºC- or a single bond, preferably one or more of them denote a single bond, particularly preferably all denote a single bond and
20 to independently of one another, denote
35 preferably P19228 AT
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- 42 -
5
R81 and R82, independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to
10 10, C atoms, preferably unfluorinated alkyl or alkenyl, one of Z81 and Z82 denotes trans-Cb=Cb-, frans-CF=CF- or -CºC- and the other, independently thereof, denotes trans-Cb=Cb-, frans-CF=CF- or a single bond, preferably one of them denotes -CºC- or trans-
15 CH=CH- and the other denotes a single bond, and
20 independently of one another, denote
25
35
I _ 91 denotes R91 or X91 ,
L92 denotes R92 or X92, P19228 AT
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- 43 -
R91 and R92, independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to
5 10, C atoms, preferably unfluorinated alkyl or alkenyl,
X91 and X92, independently of one another, denote H, F, Cl, -CN, -NCS, -SFs, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated or fluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms,
10 preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and
Z91 to Z93, independently of one another, denote frans-CH=CH-, trans- CF=CF-, -CºC- or a single bond, preferably one or more of them denotes a single bond, and particularly preferably all denote a single bond,
15 P19228 AT
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- 44 - ln a preferred embodiment of the present invention, the liquid-crystal medium comprises one or more compounds of the formula V, preferably selected from the group of the compounds of the formulae V-1 to V-3, preferably of the formulae V-1 and/or V-2 and/or V-3, preferably of the formulae V-1 and V-2:
15 in which the occurring groups have the respective meanings indicated above for formula V and preferably
R51 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms,
20 R52 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms or unfluorinated alkoxy having 1 to 7 C atoms,
X51 and X52, independently of one another, denote F, Cl, -OCF3, -CF3, -CN or -SF5, preferably F, Cl, -OCF3 or -CN.
25
The compounds of the formula V-1 are preferably selected from the group of the compounds of the formulae V-1a to V-1d, preferably V-1c and V-1d :
35 P19228 AT
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- 45 - in which the parameters have the respective meanings indicated above for formula V-1
15 and in which
Y51 and Y52, in each case independently of one another, denote H or F, and preferably
R51 denotes alkyl or alkenyl, and
X51 denotes F, Cl or -OCF3.
20
The compounds of the formula V-2 are preferably selected from the group of the compounds of the formulae V-2a to V-2e and/or from the group of the compounds of the formulae V-2f and V-2g: P19228 AT
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- 46 - where in each case the compounds of the formula V-2a are excluded from the compounds of the formulae V-2b and V-2c, the compounds of the formula V-2b are excluded from the compounds of the formula V-2c and the compounds of the formula V-2f are excluded from the compounds of the formula V-2g, and in which the parameters have the respective meanings indicated above for formula V-1 and in which
25 Y51 and Y52, in each case independently of one another, denote H or F, and preferably
Y51 and Y52 denotes H and the other denotes H or F, preferably likewise denotes H.
The compounds of the formula V-3 are preferably compounds of the formula V-3a:
30
V-3a
35 in which the parameters have the respective meanings indicated above for formula V-1 and in which preferably P19228 AT
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- 47 -
X51 denotes F, Cl, preferably F,
X52 denotes F, Cl or -OCF3, preferably -OCF3.
The compounds of the formula V- 1a are preferably selected from the group of the
5 compounds of the formulae V-1a-1 and V-1a-2:
R51 has the meaning indicated above and preferably denotes Cnf i, in which
20 n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
The compounds of the formula V-1b are preferably compounds of the formula V- 1 b- 1 :
25 in which
30 RS1 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
35 P19228 AT
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- 48 -
The compounds of the formula V-1c are preferably selected from the group of the compounds of the formulae V-1c-1 to V-1c-4, particularly preferably selected from the group of the compounds of the formulae V-1c-1 and V-1c-2:
20 in which
R51 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from
25 1 to 6 and particularly preferably 3 to 5.
The compounds of the formula V-1d are preferably selected from the group of the compounds of the formulae V-1d-1 and V-1d-2, particularly preferably the compound of the formula V-1d-2:
35 P19228 AT
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- 49 -
5 in which
R51 has the meaning indicated above and preferably denotes CnH2n+i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.
10
The compounds of the formula V-2a are preferably selected from the group of the compounds of the formulae V-2a-1 and V-2a-2, particularly preferably the compounds of the formula V-2a-1 :
15
20 in which
R51 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
25 R52 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)Z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
30
Preferred combinations of R51 with R52, in particular in the case of formula V-2a-1, are (CnH2n+i and CmH2m+i), (CnH2n+i and 0-CmH2m+i), (CH2=CH-(CH2)Z and CmH2m+i), (CH2=CH-(CH2)Z and 0-CmH2m+1) and (CnH2n+1 and (CH2)Z-CH=CH2).
35
Preferred compounds of the formula V-2b are the compounds of the formula V-2b-1 : P19228 AT
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- 50 -
5 in which
R51 has the meaning indicated above and preferably denotes CnH2n+i or
CH2=CH-(CH2)Z, and
R52 has the meaning indicated above and preferably denotes CmH2m+i or
0-CmH2m+i or (CH2)Z-CH=CH2, and in which
10 n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The preferred combination of R51 with R52 here is, in particular, CnH2n+i and CmH2m+i.
15 Preferred compounds of the formula V-2c are the compounds of the formula V-2c-1:
20 in which
R51 has the meaning indicated above and preferably denotes CnH2n+i or
CH2=CH-(CH2)Z, and
R52 has the meaning indicated above and preferably denotes CmH2m+i or
0-CmH2m+i or (CH2)Z-CH=CH2, and in which
25 n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
30 The preferred combination of (R51 and R52) here is, in particular, (CnH2n+i and CmH2m+i).
Preferred compounds of the formula V-2d are the compounds of the formula V-2d-1 :
V-2d-1 in which P19228 AT
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- 51 -
R51 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
R52 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)Z-CH=CH2, and in which
5 n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combination of (R51 and R52) here is, in particular, (CnH2n+i and CmH2m+i).
10 Preferred compounds of the formula V-2e are the compounds of the formula V-2e-1 : in which
15
R51 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
R52 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
20
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combination of (R51 and R52) here is, in particular, (CnH2n+i and 0-CmH2m+i).
Preferred compounds of the formula V-2f are the compounds of the formula V-2f-1 : in which
R51 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
35 R52 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which P19228 AT
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- 52 - n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
5
The preferred combinations of (R51 and R52) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
Preferred compounds of the formula V-2g are the compounds of the formula V-2g-1 :
10 in which
R51 has the meaning indicated above and preferably denotes CnH2n+i
15 or CH2=CH-(CH2)Z, and
R52 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly
20 preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R51 and R52) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and 0-CmH2m+i).
The compounds of the formula VI are preferably selected from the group of the compounds of the formulae VI-1 to VI-5:
VI-1
30
35
VI-3 P19228 AT
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- 53 - in which Z61 and Z62 denote -CºC-, trans- CH=CH- or trans- CF=CF-, preferably -CºC- or trans- CH=CH-, and the other occurring groups and
10 parameters have the meaning given above under formula VI, and preferably R61 and R62, independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms,
15
X62 denotes F, Cl, -OCF3 or -CN,
The compounds of the formula VI-1 are preferably selected from the group of the compounds of the formulae VI-1 a and VI-1 b, more preferably selected from
20 compounds of the formula VI-1 a:
25 in which
R61 has the meaning indicated above and preferably denotes Cnf i
30 or CH2=CH-(CH2)Z, and
R62 has the meaning indicated above and preferably denotes CmFhm+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
35 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2. P19228 AT
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The preferred combinations of (R61 and R62) here are, in particular, (Cnf i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), in the case of formula Vl-1a particularly preferably (CnH2n+i and CmH2m+i) and in the case of formula VI-1 b particularly
5 preferably (CnH2n+i and 0-CmH2m+i).
The compounds of the formula VI-3 are preferably selected from the compounds of the formula Vl-3a to Vl-3e:
30 in which the parameters have the meaning given above under formula VI-3 and preferably
R61 has the meaning indicated above and preferably denotes CnH2n+i, in which
35 n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 5, and
X62 denotes -F, -Cl, -OCF3, or -CN. P19228 AT
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- 55 -
The compounds of the formula VI-4 are preferably selected from compounds of the for mulae Vl-4a to Vl-4e:
25 in which the parameters have the meaning given above under formula VI-4 and preferably
R61 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range
30 from 1 to 5, and
X62 denotes F, Cl, OCF3, or -CN.
The compounds of the formula VI-5 are preferably selected from the compounds of the
35 formulae Vl-5a to Vl-5d, preferably Vl-5b: P19228 AT
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- 56 - in which the parameters have the meaning given above under formula VI-5 and preferably
20 R61 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 5, and
X62 denotes -F, -Cl, -OCF3, or -CN, particularly preferably -OCF3.
25
The compounds of the formula VII are preferably selected from the group of the compounds of the formulae VI 1-1 to VII-6:
35 P19228 AT
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- 57 - where the compounds of the formula VII-5 are excluded from the compounds of the formula VII-6, and in which the parameters have the respective meanings indicated above for formula VII,
Y71, Y72, Y73 independently from one another, denote H or F,
25 and preferably
R71 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms,
R72 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms,
30 or unfluorinated alkenyl having 2 to 7 C atoms,
X72 denotes F, Cl; NCS or -OCF3, preferably F or NCS, and particularly preferably
R71 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and P19228 AT
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- 58 -
R72 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly
5 preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The compounds of the formula VI 1-1 are preferably selected from the group of the compounds of the formulae VI 1-1 a to VI 1-1 d:
10 in which X72 has the meaning given above for formula VII-2 and
30 R71 has the meaning indicated above and preferably denotes Cnf i, in which n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
35 z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2, and
X72 preferably denotes F. P19228 AT
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- 59 -
The compounds of the formula VI 1-2 are preferably selected from the group of the compounds of the formulae VI l-2a and Vll-2b, particularly preferably of the formula VII- 2a: in which
R71 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and
R72 has the meaning indicated above and preferably denotes CmFhm+i
15 or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
20
The preferred combinations of (R71 and R72) here are, in particular, (Cnf i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VII-3 are preferably compounds of the formula VI l-3a:
25 R \ _ r r\ R72 Vll-3a in which
R71 has the meaning indicated above and preferably denotes Cnf i
30 or CH2=CH-(CH2)Z, and
R72 has the meaning indicated above and preferably denotes CmFhm+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
35 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2. P19228 AT
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- 60 -
The preferred combinations of (R71 and R72) here are, in particular, (Cnf i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VII-4 are preferably compounds of the formula VI l-4a:
5 F R " V-f V-TV-rV-" VI l-4a in which
R71 has the meaning indicated above and preferably denotes Cnf i
10 or CH2=CH-(CH2)Z, and
R72 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly
15 preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R71 and R72) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i)·
The compounds of the formula VII-5 are preferably selected from the group of the compounds of the formulae VI l-5a and Vll-5b, more preferably of the formula VI l-5a:
R F F\ F rt« -0-0-0-R» VI l-5b
30 in which
R71 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and
35 R72 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which P19228 AT
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- 61 - n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
5
The preferred combinations of (R71 and R72) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VII-6 are preferably selected from the group of the
10 compounds of the formulae VI l-6a and Vll-6b:
15
VI l-6b in which
20
R71 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
R72 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
25
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
30 The preferred combinations of (R71 and R72) here are, in particular, (CnH2n+i and
CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VII-7 are preferably selected from the group of the compounds of the formulae VI l-7a to VI l-7d:
35 P19228 AT
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- 62 - in which
R71 has the meaning indicated above and preferably denotes Cnf i
20 or CH2=CH-(CH2)Z,
X72 denotes F, -OCF3 or -NCS, n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
25 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The compounds of the formula VIII are preferably selected from the group of the compounds of the formulae VIII-1 to VIII-3, more preferably these compounds of the formula VIII predominantly consist, even more preferably essentially consist and very 30 particularly preferably completely consist thereof:
35 P19228 AT
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- 63 - in which
10 one of Y81 and Y82 denotes H and the other denotes H or F, and
R81 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
15 R82 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
20 z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R81 and R82) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VI 11-1 are preferably selected from the group of the compounds of the formulae VI 11-1 a to VIIMc: VII 1-1 a
30
VII 1-1 b
35 P19228 AT
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- 64 -
VIII-1C in which
RS1 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
R82 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
10 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R81 and R82) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VIII-2 are preferably compounds of the formula VI ll-2a: in which
R81 has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)Z, and
25
R82 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and
30 z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R81 and R82) here are, in particular, (CnH2n+i and CmH2m+i), (CnH2n+i and 0-CmH2m+1) and (CH2=CH-(CH2)Z and CmH2m+1), particularly
35 preferably (CnH2n+i and CmH2m+i).
The compounds of the formula VIII-3 are preferably compounds of the formula VI ll-3a: P19228 AT
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- 65 -
VII l-3a in which
RS1 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and
R82 has the meaning indicated above and preferably denotes CmFhm+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
10 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R81 and R82) here are, in particular, (Cnf i and CmH2m+l) and (CnH2n+1 and 0-CmH2m+l)·
The compounds of the formula IX are preferably selected from the group of the compounds of the formulae IX-1 to IX-3: in which the parameters have the respective meaning indicated above under formula IX
30 and preferably one of P19228 AT
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5 and in which
R91 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and
R92 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which
10 n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R91 and R92) here are, in particular, (Cnf i and
15 CmH2m+l) and (CnH2n+1 and 0-CmH2m+l)·
The compounds of the formula IX-1 are preferably selected from the group of the compounds of the formulae IX-1 a to IX-1 e: P19228 AT
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- 67 - in which the parameters have the meaning given above and preferably
5 R91 has the meaning indicated above and preferably denotes Cnf i, and n denotes an integer in the range from 0 to 15, preferably in the range from 1 to 7 and particularly preferably 1 to 5, and
10 X92 preferably denotes F or Cl.
The compounds of the formula IX-2 are preferably selected from the group of the compounds of the formulae IX-2a and IX-2b: in which
R91 has the meaning indicated above and preferably denotes Cnf i or CH2=CH-(CH2)Z, and
R92 has the meaning indicated above and preferably denotes CmH2m+i
25 or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
30
The preferred combination of (R91 and R92) here is, in particular, (CnH2n+i and CmH2m+i)·
The compounds of the formula IX-3 are preferably compounds of the formulae IX-3a and IX-3b:
35 P19228 AT
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R91 has the meaning indicated above and preferably denotes CnH2n+i
10 or CH2=CH-(CH2)Z, and
R92 has the meaning indicated above and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)z-CH=CH2, and in which n and m, independently of one another, denote an integer in the range from
1 to 7, preferably in the range from 2 to 6 and particularly
15 preferably 3 to 5, and z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R91 and R92) here are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n+i and 0-CmH2m+i), particularly preferably (CnH2n+i and 0-CmH2m+i).
In a preferred embodiment of the present invention the medium comprises one or more compounds of formula X in which
R101 denotes H, alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or
30 unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or alkenyl,
X101 denotes H, F, Cl, -CN, SFs, NCS, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms,
35 preferably fluorinated alkoxy, fluorinated alkenyloxy, F, Cl or NCS, particularly preferably NCS,
Y101 denotes methyl, ethyl or Cl, P19228 AT
WO 2021/116080 PCT/EP2020/085026 69 y102 denotes H, methyl, ethyl, F or Cl, preferably H or F, 101 £102 identically or differently, denote a single bond, -CH=CH-, -CF=CF- or -CºC-, alternatively denotes , and n is O or l
Preferably, the compounds of formula X are selected from the sub-formulae X-1 and X- 2
30
35 P19228 AT
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- 70 - in which the occurring groups and parameters have the meanings given above for formula X.
Particularly preferably, the media according to the invention comprise one or more compounds selected from the group of compounds of the formulae X-1-1 to X-1-9
10 P19228 AT
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- 71 -
X-1-9
5
In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula XI in which Rs denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or
15
20
, on each occurrence, independently of one another, denote in which RL, on each occurrence identically or differently,
35 denotes H, Cl or straight chain, branched or cyclic alkyl having 1 to 6 C atoms, P19228 AT
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- 72 -
LS1, LS2 identically or differently, denote H, Cl or F, RS1, RS2, identically or differently, denote H, alkyl or alkenyl, having up to
6 C atoms, or cyclopropyl, cyclobutyl, cyclopentenyl, or cyclopentyl,
5 Th1 Th2 identically or differently, denote H, alkyl or alkenyl or alkoxy, having up to 6 C atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl,
ZS1, ZS2, ZS3 identically or differently, denote -CH=CH-, -CH=CF-,
-CF=CH-, -CF=CF-, -CºC-, or a single bond,
10 a, b identically or differently, are 0 or 1.
Preferably, the compounds of formula XI are selected from the group of compounds of the formulae XI-1 to XI-24:
35 P19228 AT P19228 AT
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-74- P19228 AT in which the occurring groups have the meanings given above for formula XI and 20 preferably
Rs denotes alkyl or alkenyl having 2 to 6 C atoms, in which one or more
RS1 and RS2 identically or differently, denote H or alkyl having 1 to 6 C atoms, preferably H,
30
RS3 denotes H, F or alkyl, having up to 6 C atoms, or cyclopropyl, preferably
H, F or ethyl, very preferably H,
LS1 and LS2 identically or differently, denote H or F, preferably F.
35
Preferably, the medium according to the invention comprises one or more compounds of formula T P19228 AT
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- 76 - in which
RT denotes halogen, CN, NCS, RF, RF-0- or RF-S-, wherein
RF denotes fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms,
10 on each occurrence, independently of one another, denote
L4 and L5 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms;
ZT3, ZT4 identically or differently, denote -CH=CH-, -CF=CF-,
-CH=CF-, -CF=CH-, -CºC- or a single bond, and t is O or l
In a preferred embodiment, the liquid crystalline media according to the invention comprise one or more compounds selected from the group of compounds of the formulae T-1a to T-3b below:
30
35 P19228 AT
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- 77 -
5
CnF2n+i ( AT3 > = ( AT4) ( AT5)-NCS T-3b
CnF2n+iO-( At3 > = ( A14) — = ( A15 )-NCS T-4a
10 in which
In a particularly preferred embodiment of the present invention the media comprise one or more compounds selected from the compounds of the formulae T-1a and T-2a.
Preferred compounds of formula T-1a are selected from the group of compounds of the following sub-formulae:
35 P19228 AT
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- 78 - in which n is 1 , 2, 3 or 4, preferably 1.
15
Preferred compounds of formula T-2a are selected from the group of compounds of the following sub-formulae:
20
35 P19228 AT
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- 79 -
10 in which n is 1 , 2, 3 or 4, preferably 1.
Very preferably, the medium according to the invention comprises one or more compounds of formula T-1a-5.
The media according to the present invention comprise one or more chiral dopants. Preferably these chiral dopants have an absolute value of the helical twisting power (HTP) in the range of from 1 mht1 to 150 mht1, preferably in the range of from 10 mht1 to 100 mht1. In case the media comprise two or more chiral dopants, these may have opposite signs of their HTP-values. This condition is preferred for some specific embodiments, as it allows to compensate the chirality of the respective compounds to some degree and, thus, may be used to compensate various temperature dependent properties of the resulting media in the devices. Generally, however, it is preferred that most, preferably all of the chiral compounds present in the media according to the present invention have the same sign of their HTP-values.
Preferably the chiral dopants present in the media according to the instant application are mesogenic compounds and most preferably they exhibit a mesophase on their own.
In a preferred embodiment of the present invention, the medium comprises two or more chiral compounds which all have the same algebraic sign of the HTP.
The temperature dependence of the HTP of the individual compounds may be high or low. The temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependencies of the HTP in
35 corresponding ratios. P19228 AT
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For the optically active component, a multitude of chiral dopants, some of which are commercially available, is available to the person skilled in the art, such as, for example, cholesteryl nonanoate, R- and S-811, R- and S-1011, R- and S-2011, R- and S-3011,
R- and S-4011, or CB15 (all Merck KGaA, Darmstadt).
5
Particularly suitable dopants are compounds which contain one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups which form a mesogenic group with the chiral group.
10 Suitable chiral groups are, for example, chiral branched hydrocarbon radicals, chiral ethane diols, binaphthols or dioxolanes, furthermore mono- or polyvalent chiral groups selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acids, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or sequences of a few, preferably 1-5, amino acids.
15
Preferred chiral groups are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols, such as, for example, sorbitol, mannitol, iditol, galactitol or anhydro derivatives thereof, in particular dianhydrohexitols, such as dianhydrosorbide (1,4:3,6-dianhydro-D-sorbide, isosorbide), dianhydromannitol
20 (isosorbitol) or dianhydroiditol (isoiditol); sugar acids, such as, for example, gluconic acid, gulonic acid and ketogulonic acid; chiral substituted glycol radicals, such as, for example, mono- or oligoethylene or propylene glycols, in which one or more CH2 groups are substituted by alkyl or alkoxy; amino acids, such as, for example, alanine, valine, phenylglycine or phenylalanine, or sequences of from 1 to 5 of these amino
25 acids; steroid derivatives, such as, for example, cholesteryl or cholic acid radicals; terpene derivatives, such as, for example, menthyl, neomenthyl, campheyl, pineyl, terpineyl, isolongifolyl, fenchyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.
The media according to the present invention preferably comprise chiral dopants which are selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in DE 3425503,
DE 3534 777, DE 35 34778, DE 3534779 and DE 35 34780, DE 4342 280,
EP 01 038 941 and DE 19541 820. Examples are also compounds listed in Table F below. P19228 AT
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Chiral compounds preferably used according to the present invention are selected from the group consisting of the formulae shown below.
Particular preference is given to chiral dopants selected from the group consisting of compounds of the following formulae A-l to A-lll and A-Ch: in which
R3ii Rai2 anc| Rbi2 independently of one another, denote alkyl having 1 to 15 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by -C(RZ)=C(RZ)-, -CºC-, -0-, -
30 S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may each be replaced by F, Cl, Br, I or CN, preferably alkyl, more preferably n-alkyl, with the proviso that Ra12 is different from Rb12,
35 Ra21 and Ra22, independently of one another, denote alkyl having 1 to 15 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by -C(RZ)=C(RZ)-, -CºC-, -0-, - P19228 AT
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S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN, preferably both are alkyl, more preferably n-alkyl,
5 Ra31, Ra32and Rb32, independently of one another, denote straight-chain or branched alkyl having 1 to 15 C atoms, in which, in addition, one or more non- adjacent CH2 groups may each be replaced, independently of one another, by -C(RZ)=C(RZ)-,
-CºC-, -0-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that O
10 and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN, preferably alkyl, more preferably n-alkyl, with the proviso that Ra32 is different from Rb32;
Rz denotes H, CH3, F, Cl, or CN, preferably H or F,
15 R8 has one of the meanings of Ra11 given above, preferably alkyl, more preferably n-alkyl having 1 to 15 C atoms,
Z 8 denotes- C(0)0-, CH2O, CF2O or a single bond, preferably -C(0)0-,
A 11 is defined as A12 below, or alternatively denotes
20
25
30 A12 denotes preferably
35 P19228 AT
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L12 on each occurrence, independently of one another, denotes
10 halogen, CN, or alkyl, alkenyl, alkoxy or alkenyloxy having up to 12 C atoms and in which one or more H atoms are optionally replaced with halogen, preferably methyl, ethyl, Cl or F, particularly preferably F,
15
A21 denotes
20
A22 has the meanings given for A12
25
A31 has the meanings given for A11, or alternatively denotes
-0-
30
A32 has the meanings given for A12. n2 on each occurrence, identically or differently, is 0, 1 or 2, and n3 is 1, 2 or 3, and
35 r is 0, 1, 2, 3 or 4. P19228 AT
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Particular preference is given to dopants selected from the group consisting of the compounds of the following formulae: P19228 AT
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10 A-lll-9 in which m is, on each occurrence, identically or differently, an integer from 1 to 9 and n is, on each occurrence, identically or differently, an integer from 2 to 9.
Particularly preferred compounds of formula A are compounds of formula A- III.
20 Further preferred dopants are derivatives of the isosorbide, isomannitol or isoiditol of the following formula A-IV: P19228 AT
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(dianhydromannitol), or
(dianhydroiditol), p y ydrosorbitol, and chiral ethane diols, such as, for example, diphenylethanediol (hydrobenzoin), in particular mesogenic hydrobenzoin derivatives of the following formula A-V:
15
20 including the (S,S) enantiomers, which are not shown, in which are each, independently of one another, 1,4-phenylene, which
30 may also be mono-, di- or trisubstituted by L, or 1 ,4-cyclo- hexylene,
L is H, F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms,
35 c is 0 or 1 ,
X is CH2 or -C(O)-, P19228 AT
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Z° is -COO-, -OCO-, -CH2CH2- or a single bond, and
R° is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy having
1-12 carbon atoms.
Examples of compounds of formula IV are:
35 P19228 AT
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5
10
15
The compounds of the formula A-IV are described in WO 98/00428. The compounds of the formula A-V are described in GB-A-2, 328,207.
20 Very particularly preferred dopants are chiral binaphthyl derivatives, as described in WO 02/94805, chiral binaphthol acetal derivatives, as described in WO 02/34739, chiral TADDOL derivatives, as described in WO 02/06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group, as described in WO 02/06196 and WO 02/06195.
25
Particular preference is given to chiral compounds of the formula A-VI
X1, X2, Y1 and Y2 are each, independently of one another, F, Cl, Br, I, CN, SON, SFs, straight-chain or branched alkyl having from 1 to 25 carbon atoms, which is P19228 AT
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- 89 - unsubstituted or monosubstituted or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH2 groups may each, independently of one another, be replaced by -O-, -S-, -NH-,
NRX-, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH=CH- or -CºC- in such a way that O and/or S atoms are not bonded directly to one another, a polymerisable group or cycloalkyl or aryl having up to 20 carbon atoms, which may optionally be monosubstituted or polysubstituted by halogen, preferably F, or by a polymerisable group, x1 and x2 are each, independently of one another, 0, 1 or 2, y1 and y2 are each, independently of one another, 0, 1, 2, 3 or 4,
B1 and B2 are each, independently of one another, an aromatic or partially or fully saturated aliphatic six-membered ring in which one or more CH groups may each be replaced by N and one or more non-adjacent CH2 groups may each be replaced by O or S,
W1 and W2 are each, independently of one another, -Z1-A1-(Z2-A2)m-R, and one of the two is alternatively R1 or A3, but both are not simultaneously H, or
25 U1 and U2 are each, independently of one another, CH2, O, S, CO or CS, V1 and V2 are each, independently of one another, (CH2)n, in which from one to four non-adjacent CH2 groups may each be replaced by O or S, and one of V1 and V2 and, in the case where
30 W both are a single bond, n is 1 ,2 or 3
Z1 and Z2 are each, independently of one another, -O-, -S-, -CO-, -COO-, -OCO-, -O- 35 COO-, -CO-NRx-, -NRx-CO-, -O-CH2-, -CH2-O-,
-S-CH2-, -CH2-S-, -CF2-O-, -O-CF2-, -CF2-S-, -S-CF2-,
-CH2-CH2-, -CF2-CH2-, -CH2-CF2-, -CF2- P19228 AT
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CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -CºC-, a combination of two of these groups, where no two O and/or S and/or N atoms are bonded directly to one another, preferably -CH=CH- COO-, or -COO-CH=CH-, or a single bond,
Rx denotes alkyl having 1 to 6 C atoms,
A1, A2 and A3 are each, independently of one another, 1,4-phenylene, in which one or two non-adjacent CH groups may each be replaced by N, 1,4- cyclohexylene, in which one or two non-adjacent CH2 groups may each be replaced by O or S, 1,3-dioxolane-4,5-diyl, 1 ,4-cyclohexenylene, 1,4- bicyclo[2.2.2]octylene, piperidine-1 ,4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2,6-diyl or 1 ,2,3,4-tetrahydronaphthalene-2,6-diyl, where each of these groups may be monosubstituted or polysubstituted by L, and in addition A1 can be a single bond,
L is a halogen atom, preferably F, CN, NO2, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms, in which one or more H atoms may each be replaced by F or Cl, m is in each case, independently, 0, 1 , 2 or 3, and
R and R1 are each, independently of one another, H, F, Cl, Br, I, CN, SCN, SF5, straight-chain or branched alkyl having from 1 or 3 to 25 carbon atoms respectively, which may optionally be monosubstituted or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH2 groups may each be replaced by -O-, -S-, -NH-, -NR0-, -CO-, -COO-, -OCO-, -O- COO-, -S-CO-, -CO-S-, -CH=CH- or -CºC-, where no two O and/or S atoms are bonded directly to one another, or a polymerisable group.
Particular preference is given to chiral binaphthyl derivatives of the formula A-VI-1 in which ring B, R° and Z° are as defined for the formulae A-IV and A-V, and b is 0, 1 , or 2,
35 in particular those selected from the following formulae A-VI-1 a to A-VI-1 c: P19228 AT
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- 91 - in which ring B, R0· and Z° are as defined for the formula A-VI-1, and
R° as defined for formula A-IV or H or alkyl having from 1 to 4 carbon atoms, and b is 0, 1 or 2, and Z° is, in particular, -OC(O)- or a single bond.
The concentration of the one or more chiral dopant(s), in the LC medium is preferably in the range from 0.001 % to 20 %, preferably from 0.05 % to 5 %, more preferably from 0.1 % to 2 %, and, most preferably from 0.5 % to 1.5 %. These preferred concentration ranges apply in particular to the chiral dopant S-4011 or R-4011 (both from Merck KGaA) and for chiral dopants having the same or a similar HTP. For Chiral dopants having either a higher or a lower absolute value of the HTP compared to S- 4011 these preferred concentrations have to be decreased, respectively increased proportionally according to the ratio of their HTP values relatively to that of S-4011.
The pitch p of the LC media or host mixtures according to the invention is preferably in
35 the range of from 5 to 50 mhi, more preferably from 8 to 30 mhi and particularly preferably from 10 to 20 mhi. P19228 AT
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Preferably, the media according to the invention, comprise a stabilizer selected from the group of compounds of the formulae ST-1 to ST-18. P19228 AT
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35 P19228 AT
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RST denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by -CºC-, -CF2O-, -OCF2-,
-CH=CH-, - - - ~ - > -0-, -CO-O-, -O-CO- in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by halogen,
35 P19228 AT -CH=CH-CH20-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -CºC- or a single bond,
U and L2 each, independently of one another, denote F, Cl, CF3 or CHF2, P denotes 1 or 2, and
35 q denotes 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. P19228 AT
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Of the compounds of the formula ST, special preference is given to the compounds of the formulae
5
ST-1
10
ST-2a in which n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 1 or 7
15
20
25 in which n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 3
35 P19228 AT
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In the compounds of the formulae ST-3a and ST-3b, n preferably denotes 3. In the compounds of the formula ST-2a, n preferably denotes 7.
Very particularly preferred mixtures according to the invention comprise one or more 5 stabilizers from the group of the compounds of the formulae ST-2a-1 , ST-3a-1 , ST-3b-1, ST-8-1, ST-9-1 and ST-12: P19228 AT
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10
The compounds of the formulae ST-1 to ST-18 are preferably each present in the liquid-crystal mixtures according to the invention in amounts of 0.005 - 0.5%, based on the mixture.
If the mixtures according to the invention comprise two or more compounds from the group of the compounds of the formulae ST-1 to ST-18, the concentration correspondingly increases to 0.01 - 1% in the case of two compounds, based on the mixtures.
However, the total proportion of the compounds of the formulae ST-1 to ST-18, based on the mixture according to the invention, should not exceed 2%.
Other mesogenic compounds which are not explicitly mentioned above can optionally and advantageously also be used in the media in accordance with the present invention. Such compounds are known to the person skilled in the art.
In a preferred embodiment of the present invention, the total concentration of compounds of formula C in the liquid-crystalline medium is 5 % or more, preferably 8 % or more, very preferably 10% or more and particularly preferably 12 % or more.
In a preferred embodiment of the present invention, the liquid-crystalline media preferably comprise in total 2 % to 40 %, preferably 5 % to 30 % and particularly preferably 8 % to 25 % of compounds of formula C.
In a preferred embodiment of the present invention, the liquid-crystalline media comprise in total 5 % to 45 %, preferably 10 % to 40 % and particularly preferably 21/116080 PCT/EP2020/085026
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15 % to 35 % of one or more compounds of formula T, preferably selected from the formulae T-1a and T-2a, very preferably from T-1a-5 and T-2a-4.
In a preferred embodiment of the present invention, the liquid-crystalline media comprise in total 5 % to 35 %, preferably 10 % to 30 % and particularly preferably 15 % to 25 % of one or more compounds of the formula T-1a.
In a preferred embodiment of the present invention, the liquid-crystalline media comprise in total 5 % to 35 %, preferably 10 % to 30 % and particularly preferably 15 % to 25 % of one or more compounds of the formula T-1a, and in addition 5 to 15% of one or more compounds of the formula T-2a-4.
In a preferred embodiment, the medium comprises one or more compounds of formula I, preferably of formula I-2 or I-3, in a total concentration in the range of from 1 % to 25 %, more preferably from 2 % to 20 %, and particularly preferably from 5 % to 15 %.
In a preferred embodiment of the present invention the medium comprises one or more compounds of formula II, preferably of formula 11-1, in a total concentration of 5 % to 35 %, more preferably 10 % to 30 %, particularly preferably 15 % to 25 %.
In a preferred embodiment of the present invention the medium comprises one or more compounds of formula IIA-1 in a total concentration of 5 % to 25 %, more preferably 8 % to 20 %, particularly preferably 12 % to 17 %.
In a preferred embodiment of the present invention the medium comprises one or more compounds of formula 11-1 in an total concentration of 30% or less, more preferably 25% or less, particularly preferably 20% or less.
In a preferred embodiment of the present invention the medium comprises one or more compounds of formula III, preferably ill-1 and/or ill-2, more preferably 111-1 h and/or Ill- lb, in a total concentration of 15 % to 70 %, more preferably 25 % to 60 %, particularly preferably 35 % to 50 %.
In a preferred embodiment, the medium comprises one or more compounds of the formulae C and I and II and/or IIA, and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more. P19228 AT
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In a preferred embodiment, the medium comprises one or more compounds of the formulae C and II and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more.
5
In a preferred embodiment, the medium comprises one or more compounds of the formulae C and I and III and T, preferably in a total concentration of 90% or more, more preferably 95%, 96% or 97% or more, very preferably 98% or more and in particular 99% or more.
10
Further preferred embodiments of the present invention, taken alone or in combination with one another, are as follows, wherein some compounds are abbreviated using the acronyms given in Table C below:
The medium comprises one, two, three, four or more compounds of formula 111-1 ,
15 preferably selected from the compounds of the formulae 111-1 b, lll-1f and lll-1h; more preferably of 111-1 b and II 1-1 h;
The medium comprises a compound of formula 111- 1b, preferably in a total concentration in the range of from 5% to 35%, more preferably 10% to 30%, in particular 15% to 25%;
20 The medium comprises a compound of formula lll-1h, preferably in a total concentration in the range of from 10% to 40%, more preferably 15% to 35%, in particular 18% to 30%;
The medium comprises the compound PPU-TO-S and/or PPTU-TO-S and/or PTPU-TO-S and/or PP(1)TO-n-S;
25 The medium comprises one or more compounds of formula l-2d, preferably the compounds PGU-2-S and/or PGU-3-S and/or PGU-4-S, and/or CPU-2-S and/or CPU-3-S and/or CPU-4-S;
The medium comprises one or more compounds of formula l-2d and formula 11-1 b, preferably the compounds PGU-3-S and/or PGU-4-S and PTU-3-S and/or PTU-4-S
30 and/or PTU-5-S;
The medium comprises one or more compounds of formula PPTU-n-S and/or PTPU-n-S in an total concentration in the range of from 15 to 25 %;
The medium comprises one or more compounds of formula PPTU-n-S and/or PTPU-n-S and/or PGTU-n-S in a total concentration in the range of from 15 to
35 30 %, in which n is 1 , 2, 3, 4, 5, or 6; P19228 AT
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The medium comprises one or more compounds of formula ST-3, preferably ST-3a and/or ST-3b, particularly preferably ST-3b-1, in a total concentration in the range of from 0.01 to 1%, preferably from 0.05 to 0.5%, particularly from 0.10 to 0.15%.
The liquid-crystal media in accordance with the present invention preferably have a clearing point of 90°C or more, more preferably 100°C or more, more preferably 110°C or more, more preferably 120°C or more, more preferably 130°C or more, particularly preferably 140°C or more and very particularly preferably 150°C or more.
The liquid-crystal media in accordance with the present invention preferably have a clearing point of 160°C or less, more preferably 140°C or less, particularly preferably 120°C or less, and very particularly preferably 100°C or less.
The nematic phase of the media according to the invention preferably extends at least from 0°C or less to 90°C or more. It is advantageous for the media according to the invention to exhibit even broader nematic phase ranges, preferably at least from -10°C or less to 120°C or more, very preferably at least from -20°C or less to 140°C or more and in particular at least from -30°C or less to 150°C or more, very particularly preferably at least from -40°C or less to 170°C or more.
The De of the liquid-crystal medium according to the present invention, at 1 kHz and 20°C, is preferably 5 or more, more preferably 7 or more and very preferably 10 or more.
The birefringence (Dh) of the liquid-crystal media according to the present invention, at 589 nm (NaD) and 20°C, is preferably 0.280 or more, more preferably 0.300 or more, even more preferably 0.320 or more, very preferably 0.330 or more and in particular 0.350 or more.
The Dh of the liquid-crystal media according to the present invention, at 589 nm (NaD) and 20°C, is preferably in the range from 0.200 to 0.900, more preferably in the range from 0.250 to 0.800, even more preferably in the range from 0.300 to 0.700 and very particularly preferably in the range from 0.350 to 0.600.
35 P19228 AT
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In a preferred embodiment of the present application, the Dh of the liquid-crystal media in accordance with the present invention is preferably 0.50 or more, more preferably 0.55 or more.
The compounds of the formulae I to III in each case include dielectrically positive compounds having a dielectric anisotropy of greater than 3, dielectrically neutral compounds having a dielectric anisotropy of less than 3 and greater than -1.5 and dielectrically negative compounds having a dielectric anisotropy of -1.5 or less.
The compounds of the formulae C, I, II and III are preferably dielectrically positive.
In the present application, the expression dielectrically positive describes compounds or components where De > 3.0, dielectrically neutral describes those where -1.5 < De < 3.0 and dielectrically negative describes those where De < -1.5. De is determined at a frequency of 1 kHz and at 20°C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10 %, the concentration is reduced to 5 %. The capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 pm. The voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.
De is defined as (e 1 1 - e±), while e3nq. is (e 1 1 + 2 e±) / 3.
The host mixture used for the determination of physical constants of pure compounds by extrapolation is ZLI-4792 from Merck KGaA, Germany. The absolute values of the dielectric constants, the birefringence (Dh) and the rotational viscosity (gi) of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds. The concentration in the host is 10 % or in case of insufficient solubility 5 %. The values are extrapolated to a concentration of 100 % of the added compounds.
35 In the examples, the phase sequences of pure compounds are given using the following abbreviations: 21/116080 PCT/EP2020/085026
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K: crystalline, N: nematic, SmA: smectic A, SmB: smectic B, I: isotropic.
Components having a nematic phase at the measurement temperature of 20°C are measured as such, all others are treated like compounds.
The expression threshold voltage in the present application refers to the optical threshold and is quoted for 10 % relative contrast (Vio), and the expression saturation voltage refers to the optical saturation and is quoted for 90 % relative contrast (Vgo), in both cases unless expressly stated otherwise. The capacitive threshold voltage (Vo), also called the Freedericks threshold (VFr), is only used if expressly mentioned.
The parameter ranges indicated in this application all include the limit values, unless expressly stated otherwise.
The different upper and lower limit values indicated for various ranges of properties in combination with one another give rise to additional preferred ranges.
Throughout this application, the following conditions and definitions apply, unless expressly stated otherwise. All concentrations are quoted in per cent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees. All physical properties are determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and are quoted for a temperature of 20°C, unless expressly stated otherwise. The optical aniso tropy (Dh) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (De) is determined at a frequency of 1 kHz. The threshold voltages, as well as all other electro- optical properties, are determined using test cells produced at Merck KGaA, Germany. The test cells for the determination of De have a cell thickness of approximately 20 pm. The electrode is a circular ITO electrode having an area of 1.13 cm2 and a guard ring. The orientation layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic orientation (e| |) and polyimide AL-1054 from Japan Synthetic Rubber, Japan, for homogeneous orientation (e±). The capacitances are determined using a Solatron 1260 frequency response analyser using a sine wave with a voltage of 0.3 Vrms. The light used in the electro-optical measurements is white light. A set-up using a commercially available DMS instrument from Autronic-Melchers, Germany, is used here. The charac teristic voltages have been determined under perpendicular observation. The threshold 21/116080 PCT/EP2020/085026
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(Vio), mid-grey (V50) and saturation (V90) voltages have been determined for 10 %,
50 % and 90 % relative contrast, respectively.
The liquid-crystalline media are investigated with respect to their properties in the microwave frequency range as described in A. Penirschke et al. “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz“, 34th European Microwave Conference - Amsterdam, pp. 545-548. Compare in this respect also A. Gaebler et al. “Direct Simulation of Material Permittivities ...", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, and DE 102004029429 A, in which a measurement method is likewise described in detail.
The liquid crystal is introduced into a polytetrafluoroethylene (PTFE) or quartz capillary. The capillary has an inner diameter of 0.5mm and an outer diameter of 0.78mm. The effective length is 2.0 cm. The filled capillary is introduced into the center of the cylindrical cavity with a resonance frequency of 19 GHz. This cavity has a length of 11.5 mm and a radius of 6 mm. The input signal (source) is then applied, and the frequency depending response of the cavity is recorded using a commercial vector network analyzer (N5227A PNA Microwave Network Analyzer, Keysight Technologies Inc. USA. For other frequencies, the dimensions of the cavity are adapted correspond ingly.
The change in the resonance frequency and the Q factor between the measurement with the capillary filled with the liquid crystal and the measurement without the capillary filled with the liquid crystal is used to determine the dielectric constant and the loss angle at the corresponding target frequency by means of equations 10 and 11 in the above-mentioned publication A. Penirschke et al., 34th European Microwave Conference - Amsterdam, pp. 545-548, as described therein.
The values for the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by alignment of the liquid crystal in a magnetic field. To this end, the magnetic field of a permanent magnet is used. The strength of the magnetic field is 0.35 tesla.
Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuit adaptive filters and others. 21/116080 PCT/EP2020/085026
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In the present application, the term compounds is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.
All mixtures according to the invention are nematic. The liquid-crystal media according to the invention preferably have nematic phases in preferred ranges given above. The expression have a nematic phase here means on the one hand that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating from the nematic phase. At high temperatures, the clearing point is measured in capillaries by con ventional methods. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage of bulk samples: The storage stability in the bulk (LTS) of the media according to the invention at a given temperature T is determined by visual inspection. 2 g of the media of interest are filled into a closed glass vessel (bottle) of appropriate size placed in a refrigerator at a predetermined temperature. The bottles are checked at defined time intervals for the occurrence of smectic phases or crystallization. For every material and at each temperature two bottles are stored. If crystallization or the appearance of a smectic phase is observed in at least one of the two correspondent bottles the test is terminated and the time of the last inspection before the one at which the occurrence of a higher ordered phase is observed is recorded as the respective storage stability. The test is finally terminated after 1000 h, i.e an LTS value of 1000 h means that the mixture is stable at the given temperature for at least 1000 h.
The liquid crystals employed preferably have a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more and very particularly preferably 10 or more.
Furthermore, the liquid-crystal media according to the invention are characterized by high anisotropy values in the microwave range. The birefringence at about 19 GHz is, for example, preferably 0.14 or more, particularly preferably 0.15 or more, particularly preferably 0.20 or more, particularly preferably 0.25 or more and very particularly preferably 0.30 or more. In addition, the birefringence is preferably 0.80 or less.
The dielectric anisotropy in the microwave range is defined as 21/116080 PCT/EP2020/085026
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The tunability (t) is defined as
X º (DbG / 8 r, I I ) .
The material quality (h) is defined as h º (t / tan de r, max ), where the maximum dielectric loss is tan de r,max. º max. { tan de r,± tan de r, 1 1 } .
The tunability t of the medium according to the invention, measured at 20°C and 19 GHz is 0.250 or more, preferably 0.300 or more, 0.310 or more, 0.320 or more, 0.330 or more, or 0.340 or more, very preferably 0.345 or more and in particular 0.350 or more.
The material quality (h) of the preferred liquid-crystal materials is 6 or more, preferably 8 or more, preferably 10 or more, preferably 15 or more, preferably 17 or more, preferably 20 or more, particularly preferably 25 or more and very particularly preferably 30 or more.
In the corresponding components, the preferred liquid-crystal materials have phase shifter qualities of 15 dB or more, preferably 207dB or more, preferably 307dB or more, preferably 407dB or more, preferably 507dB or more, particularly preferably 807dB or more and very particularly preferably 1007dB or more.
In some embodiments, however, liquid crystals having a negative value of the dielectric anisotropy can also advantageously be used.
The liquid crystals employed are either individual substances or mixtures. They preferably have a nematic phase.
The liquid-crystal media in accordance with the present invention may comprise further additives and chiral dopants in the usual concentrations. The total concentration of 21/116080 PCT/EP2020/085026
- 109 - these further constituents is in the range from 0 % to 10 %, preferably 0.1 % to 6 %, based on the mixture as a whole. The concentrations of the individual compounds used are each preferably in the range from 0.1 % to 3 %. The concentration of these and similar additives is not taken into consideration when quoting the values and concentration ranges of the liquid-crystal components and liquid-crystal compounds of the liquid-crystal media in this application.
Preferably the media according to the present invention comprise one or more chiral compounds as chiral dopants in order to adjust their cholesteric pitch. Their total concentration in the media according to the instant invention is preferably in the range 0.05 % to 15 %, more preferably from 1 % to 10 % and most preferably from 2 % to 6 %.
Optionally the media according to the present invention may comprise further liquid crystal compounds in order to adjust the physical properties. Such compounds are known to the skilled person. Their concentration in the media according to the instant invention is preferably 0 % to 30 %, more preferably 0.1 % to 20 % and most preferably 1 % to 15 %.
The response times are given as rise time (xon) for the time for the change of the relative tuning, respectively of the relative contrast for the electro-optical response, from 0 % to 90 % (tgo - to), i.e. including the delay time ( o - to), as decay time (x0ff) for the time for the change of the relative tuning, respectively of the relative contrast for the electro-optical response, from 100 % back to 10 % (hoo - ho) and as the total response time (xtotai = xon + xoff), respectively.
The liquid-crystal media according to the invention consist of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20 and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the dissolution process. It is, however, also possible to prepare the media in other conventional ways, for example using so-called pre-mixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called “multi-bottle” systems, the constituents of which are themselves ready-to-use mixtures. P19228 AT
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All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals, are quoted in degrees Celsius. All temperature differences 5 are quoted in differential degrees.
In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations, also referred to as acronyms. In these acronyms, the chemical formulae are abbreviated as follows using 10 Tables A to D below. All groups CnH2n+1, CmH2m+1 and CIH2I+I, and CnH2n, CmH2m and
CH denote straight-chain alkyl or alkylene, respectively, in each case having n, m or I C atoms, wherein n and m, independently are 1, 2, 3, 4, 5, 6 or 7 and I is 1 , 2 or 3. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups. Table C gives the meanings of 15 the codes for the left-hand or right-hand end groups. Table D shows illustrative structures of compounds with their respective abbreviations.
Table A: Rinq elements P19228 AT
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E -CH2CH2- Z -CO-O-
V -CH=CH- Zl -O-CO-
X -CF=CH- O -CH2-O-
XI -CH=CF- Ol -O-CH2-
B -CF=CF- Q -CF2-O-
35
T -CºC- Ql -O-CF2-
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Table B: End qroups
Left-hand side Right-hand side
5 Used alone
-n- CnH2n+1" -n -CnH2n+1
-nO- CnH2n+1"0- -On -0-CnH2n+1
-V- CH2=CH- -V -CH=CH2
-nV- CnH2n+i-CH=CH- -nV -CnH2n-CH=CH2
10 -Vn- CH2=CH- CnH2n+i- -Vn -CH=CH-CnH2n+i
-nVm- CnH2n+i-CH=CH-CmH2m- -nVm -CnH2rrCH=CH-CmH2m+1
-N- NºC- -N -CºN
-S- S=C=N- -S -N=C=S
-F- F- -F -F
15 -CL- Cl- -CL -Cl
-M- CFH2- -M -CFH2
-D- CF2H- -D -CF2H
-T- CFs- -T -CFs
-MO- CFH2O- -OM -OCFH2
20 -DO- CF2HO- -OD -OCF2H
-TO- CF3O- -OT -OCFs
-FXO- CF2=CH-0- -OXF -0-CH=CF2
-A- H-CºC- -A -CºC-H
-nA- CnH2n+1-CºC- -An -CºC-CnH2n+1
25 -NA- NºC-CºC- -AN -CºC-CºN
Used in combination with others
-...A...- -CºC- -...A... -CºC-
-...Zl...- -o-co- -...Zl... -o-co-
-...K...- -co- -...K... -co-
-...W...- -CF=CF- -...W... -CF=CF-
35 in which n and m each denote integers, and the three dots are placeholders for other abbreviations from this table. P19228 AT
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The following table shows illustrative structures together with their respective abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds which are preferably used.
Table C: Illustrative structures
The following illustrative structures are compounds, which are preferably additionally used in the media:
GGP-n-S P19228 AT
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PTPU-n-S P19228 AT
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PYP-n-m
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PGU-n-CL
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10 PPU-T-S
PPTU-TO-S
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PPTU(F,F)-TO-S
PP(n)TU-TO-S
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PGIGP-n-Qm
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PGIGP-nO-m
5
F F F
CnH2n+1 0M0 GH0 CmH2m+1
PYGP-n-m
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APGP-n-m P19228 AT
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Preferably, the medium according to the invention comrises one or more compounds selected from the compounds of Table C.
5
The following table, Table D, shows illustrative compounds which can be used as alternative stabilizers in the mesogenic media in accordance with the present invention. The total concentration of these and similar compounds in the media is preferably 5 % or less.
10
Table D
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30
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In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table D.
The following table, Table E, shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media in accordance with the present invention.
Table E P19228 AT
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R/S-1011 P19228 AT
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In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds of Table E.
The mesogenic media in accordance with the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.
Examples
The following examples illustrate the present invention without limiting it in any way.
It is clear to the person skilled in the art from the physical properties what properties can be achieved and in what ranges they can be modified. In particular, the
35 combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art. P19228 AT
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Synthesis Examples
Abbreviations:
RT room temperature (typically 20°C ± 1°C)
5 THF Tetrahydrofuran
MTB ether Methyl-te/f-butyl ether
DCM Dichloromethane dist. distilled
XPhos 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl
10
XPhos Pd G2 Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1 , 1 biphenyl)[2-(2'-amino-1,T-biphenyl)palladium (II)
Example 1: 5-[4-(4-Butylphenyl)phenyl]ethynyl]-1-chloro-3-fluoro-2-isothiocyanato- benzene
Step 1: [4-(4-Butylphenyl)phenyl]ethynyl-trimethyl-silane
A mixture of 1-bromo-4-(4-butylphenyl)benzene (CAS 63619-54-5, 33.5 g, 116 mmol), triethylamine (135 ml), bis(triphenylphosphine)-palladium(ll)-chloride (3.2 g, 4.6 mmol),
25 copper(l)-iodide (530 mg, 2.8 mmol) and trimethylsilyl acetylene (33.6 ml, 237 mmol) is heated at reflux temperature overnight. Then water and MTB-ether are added to the reaction mixture. The phases are separated, and the aqueous layer is extracted with
MTB-ether. The combined organic phases are washed with dist. water, dried (sodium sulfate) and concentrated i. vac. The residue is purified by flash chromatography 30
(heptane) to give [4-(4-butylphenyl)phenyl]ethynyl-trimethyl-silane as an orange solid.
Step 2: 1-Butyl-4-(4-ethynylphenyl)benzene P19228 AT
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Tetra-n-butylammonium fluoride (113 ml, 1 M in THF) is added slowly to a solution of [4-(4-butylphenyl)phenyl]ethynyl-trimethyl-silane (34.6 g, 113 mmol) in THF (650 ml) at 10°C. The reaction mixture is stirred at RT overnight. Then water, hydrochloric acid (1 M) and MTB-ether are added. The phases are separated, and the aqueous phase is 5 extracted with MTB-ether. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by flash chromatography (heptane) to give 1-butyl-4-(4-ethynylphenyl)benzene as a light yellow solid.
10
Step 3: 4-[4-(4-Butylphenyl)phenylethynyl]-2-chloro-6-fluoro-aniline
15
20 A mixture of 1-butyl-4-(4-ethynylphenyl)benzene (4.0 g, 17 mmol) and 4-bromo-2- chloro-6-fluoro-aniline (3.9 g, 17 mmol) in diisopropylamine (40 ml) and THF (40 ml) is heated to 70°C under nitrogen atmosphere. Then XPhos PD G2 (27 mg, 0.03 mmol), XPhos (16 mg, 0.03 mmol) and copper(l)-iodide (3.3 mg, 0.02 mmol) are added, and the reaction mixture is stirred at 70°C overnight. Then it is filtered and concentrated in
25 vacuo. The residue is purified by flash chromatography (heptane and heptane/MTB- ether) to give 4-[4-(4-butylphenyl)phenylethynyl]-2-chloro-6-fluoro-aniline as a light brown solid.
Step 4: 5-[4-(4-Butylphenyl)phenyl]ethynyl]-1-chloro-3-fluoro-2-isothiocyanato-benzene
30
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Thiophosgene (1.5 ml, 19 mmol) is added dropwise to a mixture of 4-[4-(4-
10 butylphenyl)phenylethynyl]-2-chloro-6-fluoro-aniline (6.6 g, 18 mmol) and 1,4 diazabicyclo[2.2.2]octane (4.9 g, 44 mmol) in dichloromethane (70 ml) at 0°C, and the reaction mixture is stirred for 1 h at room temperature. The reaction is hydrolyzed with brine, and the phases are separated. The aqueous phase is extracted with dichloromethane, and the combined organic phases are dried (sodium sulfate) and 15 concentrated in vacuo. The residue is purified by flash chromatography (heptane) and crystallization with heptane and acetone to give 5-[4-(4-butylphenyl)phenyl]ethynyl]-1- chloro-3-fluoro-2-isothiocyanato-benzene as a pale yellow powder.
Phase sequence K 51 N 171 I.
20 De = 17.2
Dh = 0.4564 gi = 911 mPas
In analogy to Synthesis Examplel the following compounds are obtained:
25
30
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5
30
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5
30
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5
30
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5
30
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5
30
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10
15
20
25
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5
30
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5
30
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5
30
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5
30
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35 Liquid-crystal mixtures N1 to N5 having the compositions and properties as indicated in the following tables are prepared and characterized with respect to their general P19228 AT
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Example N1
5 PPTU-4-S 6.0 T(N,I) [°C]: 154.5
PPTU-5-S 13.0 t [20°C, 19 GHz]: 0.329
PPU-TO-S 22.0 8r,n [20°c, 19 GHz]: 3.67
PGU-3-S 12.0 eG,i [20°C, 19 GHz]: 2.47
10 CPTU-5-S 24.0 tan 5e r,n [20°C, 19 GHz]: 0.0052
P(2)TU-5-S 15.0 tan 5e r,± [20°C, 19 GHz]: 0.0090
PPTG(CI)-4-S 8.0 h [20°C, 19 GHz]: 36.6 å 100.0
15
Example N2
PPTU-4-S 6.0 T(N,I) [°C]: 155.5
PPTU-5-S 12.0 De [1 kHz, 20°C]: 18.1
20 PPU-TO-S 17.0 B [1 kHz, 20°C]: 22.0
CPTU-5-S 20.0 si [1 kHz, 20°C]: 3.9
PTU-3-S 10.0 gi [ Pa s, 20°C]: 595
PTU-5-S 10.0 Ki [pN, 20°C]: 18.2
25 PPTG(CI)-4-S 25.0 K3 [pN, 20°C]: 23.1 å 100.0 K3/K1 [pN, 20°C]: 1.27
V0 [V, 20°C]: 1.05 t [20°C, 19 GHz]: 0.341
30 sr, ii [20°C, 19 GHz]: 3.74
8r,i [20°C, 19 GHz]: 2.46 tan de r,n [20°C, 19 GHz]: 0.0051 tan 5e r,± [20°C, 19 GHz]: 0.0087 h [20°C, 19 GHz]: 39.4 P19228 AT
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Example N3
PPTU-4-S 6.0 T (N , I) [°C]: 163
PPTU-5-S 12.0 De [1 kHz, 20°C]: 15.5
PPU-TO-S 23.0 8|| [1 kHz, 20°C]: 19.3
5
PGU-3-S 10.0 Si [1 kHz, 20°C]: 3.8
CPTU-5-S 25.0 gi [mPa s, 20°C]: 671
PP(1)TU-TO-S 10.0 Ki [pN, 20°C]: 16.2
PTG(CI)-4-S 14.0 K3 [pN, 20°C]: 27.7
10 å 100.0 K3/Ki [pN, 20°C]: 1.70
Vo [V, 20°C]: 1.08 t [20°C, 19 GHz]: 0.341 sr, I, [20°C, 19 GHz]: 3.68
15
8r,i [20°C, 19 GHz]: 2.42 tan 5e r,n [20°C, 19 GHz]: 0.0054 tan 5e r,± [20°C, 19 GHz]: 0.0093 h [20°C, 19 GHz]: 36.7
20
Example N4
PPTU-4-S 6.0 De [1 kHz, 20°C]: 14.4
PPTU-5-S 12.0 B [1 kHz, 20°C]: 18.1
25
PPU-TO-S 23.0 si [1 kHz, 20°C]: 3.7
CPTU-5-S 25.0 gi [ Pa s, 20°C]: 630
PTG(CI)-4-S 14.0 Ki [pN, 20°C]: 15.5
PP(1)TU-TO-S 10.0 K3 [pN, 20°C]: 27.0
30
CPU-2-S 10.0 K3/K1 [pN, 20°C]: 1.74 å 100.0 Vo [V, 20°C]: 1.10 t [20°C, 19 GHz]: 0.334 sr, ii [20°C, 19 GHz]: 3.65
35
Sr.± [20°c, 19 GHz]: 2.43 P19228 AT
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5
Example N5 PTU-3-S 16.0 T(N,I) [°C]: 169.5 PPTU-4-S 10.0 De [1 kHz, 20°C]: 24.8 PPTU-5-S 20.0 B [1 kHz, 20°C]: 28.9
10
CPTU-5-S 24.0 si [1 kHz, 20°C]: 4.1
PGTU-4-S 10.0 ^ [ Pa s, 20°C]: 536
PGU-3-S 10.0 Ki [pN, 20°C]: 21.7
PTPG(CI)-4-S 10.0 K3 [pN, 20°C]: 25.3
15 - å 100.0 K3/K1 [pN, 20°C]: 1.17
Vo [V, 20°C]: 0.98
LTS bulk [h, -20° C]: 1000
LTS bulk [h, -30°C]: 408 0 t [20°C, 19 GHz]: 0.348 sr, H [20°C, 19 GHz]: 3.77
8r,± [20°C, 19 GHz]: 2.46 tan de r,n [20°C, 19 GHz]: 0.0049 5 tan 5e r,± [20°C, 19 GHz]: 0.0094 h [20°C, 19 GHz]: 37.2 0 5

Claims

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Patent Claims in which
Rc denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CF^-groups may be
10 replaced denotes a group Rp,
Rp denotes halogen, CN, NCS, RF, RF-0- or RF-S-, wherein
RF denotes fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms,
15 ZC1, ZC2 identically or differently, denote -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -CºC- or a single bond,
X denotes Cl or F,
Y denotes H, Cl, F, alkyl or alkoxy each having 1 to 6 C atoms, t is 0, 1 or 2, and
20 denote a radical selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, in
25 which one or two CH groups may be replaced by N and in which one or more H atoms may be replaced by L, b) the group consisting of trans-1 ,4-cyclohexylene, 1 ,4-cyclohexenylene, bicyclo- [1.1.1]pentane-1 ,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, in which one or more non-adjacent CH2 groups may
30 be replaced by -O- and/or -S- and in which one or more H atoms may be replaced by F, c) the group consisting of thiophene-2, 5-diyl, thieno[3,2-b]thiophene-2,5-diyl or selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L,
L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF5 or
35 straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, P19228 AT
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2. The compound according to claim 1 , wherein
5 independently of one another, denote wherein
L1 and L2 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms.
25
3. The compound according to claim 1 or 2, wherein ZC1 and ZC2, identically or differently, denote -CºC- or a single bond.
4. The compound according to one or more of claims 1 to 3, wherein the compound is
30 selected from the compounds of the formulae C-1 to C-11
35 PCT/EP2020/085026
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L1, L2 and L3 identically or differently, denote H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and Rc and X have the meanings given in claim 1.
5. The compound according to one or more of claims 1 to 4, wherein X denotes F.
15
6. The compound according to one or more of claims 1 to 5, wherein Rc denotes alkyl having 1 to 12 C atoms.
7. The compound according to one or more of claims 1 to 5, wherein the group Rc denotes Rp as defined in claim 1.
8. A liquid crystal medium comprising one or more compounds according to one or more of claims 1 to 7.
9. The liquid crystal medium according to claim 8, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae I, II and III,
30 III
35 in which P19228 AT
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R1 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having
2 to 15 C atoms, in which one or more CH2-groups may be replaced by to on each occurrence, independently of one another, denote
25 in which RL, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms, and wherein
R2 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having P19228 AT
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- 156 -
2 to 15 C atoms, in which one or more CH2-groups may be replaced by
Z21 denotes frans-CH=CH-, frans-CF=CF- or -CºC-, and
10 independently of one another, denote in which RL, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms;
25
R3 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having
2 to 15 C atoms, in which one or more CH2-groups may be replaced by
30 one of Z31 and Z32 , denotes frans-CH=CH-, frans-CF=CF- or -CºC- and the other one, independently thereof, denotes -CºC-, frans-CH=CH-, frans-CF=CF- or a single bond, and
35 P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 157 - to independently of one another, denote
5 in which RL, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms, and wherein
20
10. The liquid-crystal medium according to claim 8 or 9, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae 1-1 to I-5 P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 158 - in which
U, L2 and L3 on each occurrence, identically or differently, denote H or F, and
15
R1 have the meanings given for formula I in claim 9.
11. The liquid-crystal medium according to one or more of claims 8 to 10, wherein the medium comprises one or more compounds selected from the group of compounds of
20 the formulae 11-1 to II-3
35 12. Liquid-crystal medium according to one or more of claims 8 to 11, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae 111-1 to III-6 P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 159 -
10 IN-4
R A31)— Z3 A32)— ( A33) NCS
IM-5
15
RH A31)— Z3 A32) Z32— A33)— NCS
IM-6 in which have the meanings given in claim 9 for formula III, and
Z31 and Z32 independently of one another, denote frans-CH=CH- or frans-CF=CF-, and in formula ill-6 one of Z31 and Z32 alternatively denotes -CºC-.
25
13. Liquid-crystal medium according to one or more of claims 8 to 12, wherein the medium comprises one or more compounds of the formula T
30 in which
RT denotes halogen, CN, NCS, RF, RF-0- or RF-S-, wherein
RF denotes fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms, P19228 AT
WO 2021/116080 PCT/EP2020/085026
- 160 - on each occurrence, independently of one another, denote
10 L4 and L5 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms;
ZT3, ZT4 identically or differently, denote -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -CºC- or a single bond, and t is O or 15
14. Component for high-frequency technology, characterized in that it comprises the liquid crystal medium according to one or more of claims 8 to 13.
15. Component according to claim 14, wherein the component is a liquid-crystal based 20 antenna element, a phase shifter, a tunable filter, a tunable metamaterial structure, a matching network or a varactor.
16. Microwave antenna array, characterized in that it comprises one or more components according to claim 14 or 15.
25
30
35
EP20819753.3A 2019-12-10 2020-12-08 Aromatic isothiocyanates Active EP4073205B1 (en)

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